JP4991311B2 - Herbicidal pyrimidine - Google Patents

Description

  The present invention relates to certain pyrimidines, their N-oxides, agriculturally suitable salts and compositions, and methods for their use to control undesirable vegetation.

  In order to achieve high crop efficiency, the suppression of undesirable vegetation is very important. It is highly desirable to achieve selective control of weed growth, especially in useful crops such as rice, soybeans, sugar beets, corn (corn), potatoes, wheat, barley, tomatoes and especially plantation crops. The inability to control weed growth in such useful crops can cause a significant decrease in productivity and thereby increase costs to consumers. Control of undesirable vegetation in non-crop areas is also important. Many products are available commercially for these purposes, but new compounds that are more effective, less expensive, less toxic, environmentally safer, or have different modes of action Is still needed.

  Patent Document 1 discloses a pyrimidine useful as a plant protective agent, particularly as a bactericidal / fungicidal agent. Patent Document 2 discloses pyrimidine as a plant growth regulator. Patent Document 3 discloses sulfonated heterocyclic carboxamide derivatives of pyrimidine as herbicides and growth regulators.

International Publication No. WO92 / 05159-A Pamphlet European Patent Application Publication No. EP-136976-A2 US Pat. No. 5,324,710

SUMMARY OF THE INVENTION The present invention relates to compounds of formula I including all geometric and stereoisomers, their N-oxides or agriculturally suitable salts, agricultural compositions containing them and their as herbicides. Regarding use.

[Where:
R ¹ is cyclopropyl optionally substituted by 1 to 5 R ⁵ , isopropyl optionally substituted by 1 to 5 R ⁶ , or optionally 1 to 3 R ⁷ Phenyl optionally substituted by
R ² is ((O) _j C (R ¹⁵ ) (R ¹⁶ )) _k R;
R is CO ₂ H or a herbicidally effective derivative of CO ₂ H;
R ³ is halogen, cyano, nitro, OR ²⁰ , SR ²¹ or N (R ²² ) R ²³ ;
R ⁴ is —N (R ²⁴ ) R ²⁵ or —NO ₂ ;
Each R ⁵ and R ⁶ is independently halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₁ -C ₃ alkoxy, C ₁ -C _{2 haloalkoxy,} a C 1 -C ₃ alkylthio or _C 1 -C ₂ haloalkylthio,
Each R ⁷ is independently halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₄ hydroxy _alkyl, C 2 -C _{4 alkoxyalkyl,} C 2 -C ₄ halo _alkoxyalkyl, C 2 -C _{4 alkenyl,} C 2 -C _{4 haloalkenyl,} C 3 -C _{4 alkynyl,} C 3 -C ₄ haloalkynyl, hydroxy C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₂ -C ₄ alkenyloxy, C ₂ -C ₄ haloalkenyloxy, C ₃ -C ₄ alkynyloxy, C ₃ -C ₄ haloalkynyloxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ haloalkylsulfur _Iniru, C 1 -C _{4 alkylsulfonyl,} C 1 -C _{4 haloalkylsulfonyl,} C 2 -C _{4 alkenylthio,} C 2 -C ₄ halo alkenylene _thio, C 2 -C _{4 alkenylsulfinyl,} C 2 -C ₄ haloalkenyl _sulfinyl, C 2 -C _{4 alkenylsulfonyl,} C 2 -C ₄ haloalkenyl _sulfonyl, C 3 -C _{4 alkynylthio,} C 3 -C ₄ halo alkynylene _thio, C 3 -C _{4 alkynylsulfinyl,} C 3 -C ₄ halo _{alkynylsulfinyl,} C 3 -C _{4 alkynylsulfonyl,} C 3 -C ₄ haloalkynyl _sulfonyl, C 1 -C _{4 alkylamino,} C 2 -C _{8 dialkylamino,} C 3 -C _{6 cycloalkylamino,} C 4 -C ₆ (alkyl) _{cycloalkylamino,} C 2 -C ₆ alkylcarbonyl, C -C _{6 alkoxycarbonyl,} C 2 -C _{6 alkylaminocarbonyl,} a C 3 -C _{8 dialkylaminocarbonyl,} C 3 -C ₆ trialkylsilyl, phenyl, phenoxy and 5- or 6-membered aromatic heterocyclic Each phenyl, phenoxy and 5- or 6-membered aromatic heterocycle may be optionally substituted by 1 to 3 substituents independently selected from R ⁴⁵ , or two adjacent R ⁷ together —OCH ₂ O—, —CH ₂ CH ₂ O—, —OCH (CH ₃ ) O—, —OC (CH ₃ ) ₂ O—, —OCF ₂ O—, —CF ₂ CF ₂ O—, —OCF ₂ CF ₂ O— or —CH═CH—CH═CH—,
R ¹⁵ is H, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, hydroxy, C ₁ -C ₄ alkoxy or C ₂ -C ₄ alkylcarbonyloxy;
R ¹⁶ is H, halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl, or R ¹⁵ and R ¹⁶ are oxygen atoms, together with the carbon atom to which they are attached, a carbonyl moiety Form the
R ²⁰ is H, C ₁ -C ₄ alkyl or C ₁ -C ₃ haloalkyl,
R ²¹ is H, C ₁ -C ₄ alkyl or C ₁ -C ₃ haloalkyl,
R ²² and R ²³ are independently H or C ₁ -C ₄ alkyl;
R ²⁴ is H, C ₁ -C ₄ alkyl optionally substituted by 1 to 2 R ³⁰ , C ₂ -C ₄ alkenyl optionally substituted by 1 to 2 R ³¹ Or C ₂ -C ₄ alkynyl optionally substituted by 1 to 2 R ³² , or R ²⁴ is C (═O) R ³³ , nitro, OR ³⁴ , S (O) _2. R ³⁵ , N (R ³⁶ ) R ³⁷ or N = C (R ⁶² ) R ⁶³ ,
R ²⁵ is H, C ₁ -C ₄ alkyl or C (═O) R ³³ optionally substituted by 1 to 2 R ³⁰ , or R ²⁴ and R ^{25 taken} together — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, —CH ₂ CH═CHCH ₂ — and — (CH ₂ ) ₂ O (CH ₂ ) ₂ —, each group is May be substituted by 1 to 2 R ³⁸ , or R ²⁴ and R ²⁵ together may be ═C (R ³⁹ ) N (R ⁴⁰ ) R ⁴¹ or ═C (R ⁴² ) OR ⁴³ Yes,
Each ^{R 30, R 31} and ^{R 32} are independently _halogen, C 1 -C _{3 alkoxy,} C 1 -C _{3 haloalkoxy,} C 1 -C _{3 alkylthio,} C 1 -C ₃ haloalkylthio, _{amino, C} 1 ~ C ₃ alkylamino, C ₂ -C ₄ dialkylamino or C ₂ -C ₄ alkoxycarbonyl,
Each R ³³ is independently H, C ₁ -C ₁₄ alkyl, C ₁ -C ₃ haloalkyl, C ₁ -C ₄ alkoxy, phenyl, phenoxy or benzyloxy;
R ³⁴ is H, C ₁ -C ₄ alkyl, C ₁ -C ₃ haloalkyl or CHR ⁶⁶ C (O) OR ⁶⁷ ;
R ³⁵ is C ₁ -C ₄ alkyl or C ₁ -C ₃ haloalkyl;
R ³⁶ is H, C ₁ -C ₄ alkyl or C (═O) R ⁶⁴ ,
R ³⁷ is H or C ₁ -C ₄ alkyl;
Each R ³⁸ is independently halogen, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, C ₁ -C ₃ haloalkoxy, C ₁ -C ₃ alkylthio, C ₁ -C ₃ haloalkylthio, amino, C ₁ -C _{3 alkylamino,} a C 2 -C ₄ dialkylamino or _C 2 -C ₄ alkoxycarbonyl,
R ³⁹ is H or C ₁ -C ₄ alkyl;
R ⁴⁰ and R ⁴¹ are independently H or C ₁ -C ₄ alkyl, or R ⁴⁰ and R ^{41 taken} together are — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, —CH ₂ CH═CHCH ₂ — or — (CH ₂ ) ₂ O (CH ₂ ) ₂ —,
R ⁴² is H or C ₁ -C ₄ alkyl;
R ⁴³ is C ₁ -C ₄ alkyl;
Each R ⁴⁵ is independently halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₂ -C ₄ alkenyl. , _C 2 -C _{4 haloalkenyl,} C 3 -C _{4 alkynyl,} C 3 -C _{4 haloalkynyl,} C 1 -C _{4 alkoxy,} C 1 -C _{4 haloalkoxy,} C 1 -C _{4 alkylthio,} C 1 -C _{4 haloalkylthio,} C 1 -C _{4 alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl,} C 1 -C _{4 alkylamino,} C 2 -C _{8 dialkylamino,} C 3 -C _{6 cycloalkylamino,} C 4 -C ₆ (alkyl) _{cycloalkylamino,} C 2 -C _{4 alkylcarbonyl,} C 2 -C _{6 alkoxycarbonyl,} C 2 -C ₆ alkylamino Cal _Alkenyl, a C 3 -C ₈ dialkylaminocarbonyl or _C 3 -C ₆ trialkylsilyl,
R ⁶² is H, C ₁ -C ₄ alkyl or phenyl optionally substituted by 1 to 3 R ⁶⁵ ,
R ⁶³ is H or C ₁ -C ₄ alkyl, or R ⁶² and R ⁶³ together are — (CH ₂ ) ₄ — or — (CH ₂ ) ₅ —,
R ⁶⁴ is H, C ₁ -C ₁₄ alkyl, C ₁ -C ₃ haloalkyl, C ₁ -C ₄ alkoxy, phenyl, phenoxy or benzyloxy;
Each R ⁶⁵ is independently CH ₃ , Cl or OCH ₃ ;
R ⁶⁶ is H, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy;
R ⁶⁷ is H, C ₁ -C ₄ alkyl or benzyl;
j is 0 or 1, and k is 0 or 1,
Where (a) when k is 0, j is 0;
(B) when R ² is CH ₂ OR ^a and R ^a is H, optionally substituted alkyl or benzyl, R ³ is other than cyano;
(C) when R ¹ is phenyl substituted at each meta position by Cl, the phenyl is also substituted at the para position by R ⁷ ;
(D) when R ¹ is phenyl substituted by R ^{7 in the} para position, said R ⁷ is other than tert-butyl, cyano or optionally substituted phenyl;
(E) when R ¹ is cyclopropyl or isopropyl optionally substituted by 1 to 5 R ⁶ , R is C (═W) N (R ^b ) S (O) ₂ —R ^c Other than -R ^d , where W is O, S, NR ^e or NOR ^e , R ^b is hydrogen, C ₁ -C ₄ alkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl. , R ^c is a direct bond or CHR ^f , O, NR ^e or NOR ^e and R ^d has 5 to 6 ring atoms and may be optionally substituted, optionally aromatic or non-aromatic 5 A heterocyclic or carbocyclic aromatic group optionally fused to a 6-membered or 6-membered ring, wherein each R ^e is independently H, C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl or phenyl. There, and ^{R f} is _H, C 1 -C ₃ An alkyl or phenyl, and (f) a compound of formula I is other than 6-amino-5-nitro-2-phenyl-4-pyrimidin-malonate]

  In particular, the invention relates to compounds of formula I including all geometric and stereoisomers, their N-oxides or agriculturally suitable salts. The invention also relates to a herbicidal composition comprising a herbicidally effective amount of a compound of formula I and at least one of a surfactant, a solid diluent or a liquid diluent. The present invention further inhibits the growth of undesirable vegetation comprising contacting the vegetation or its environment (eg, as a composition described herein) with a herbicidally effective amount of a compound of formula I. Related to the method. The present invention comprises a herbicidally effective amount of a compound of formula I and an effective amount of at least one additional active ingredient selected from the group consisting of other herbicides and herbicide safeners. It also relates to herbicidal compositions. The present invention further provides a herbicidally effective amount of a compound of formula I, an effective amount of at least one additional active ingredient selected from the group consisting of other herbicides and herbicide safeners, and a surface activity. And a herbicidal composition comprising at least one of an agent, a solid diluent and a liquid diluent.

DETAILED DESCRIPTION OF THE INVENTION As used herein, the terms “comprising”, “comprising”, “including”, “including”, “having”, “having” or Any of those other variations are intended to encompass non-exclusive inclusions. For example, a composition, process, method, article or device comprising a list of elements is not necessarily limited to those elements, but is not expressly described or such compositions, processes, methods, It may include other elements that are specific to the article or device. Further, unless stated to the contrary, “or or or” refers to inclusive OR and not exclusive OR. For example, condition A or B is met by any one of the following: A is true (or present) and B is false (or absent). A is false (or absent) and B is true (or present). And both A and B are true (or present).

  Also, the indefinite articles “a” and “an” preceding an element or component of the invention are intended to be non-limiting with respect to the number of instances (ie, the number of occurrences) of the element or component. Thus, “a” or “an” should be read to include 1 or at least 1, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.

In the above, the term “alkyl” used either alone or in combination words such as “alkylthio” or “haloalkyl” includes methyl, ethyl, n-propyl, i-propyl or various butyl, pentyl Or a linear or branched alkyl like a hexyl isomer is mentioned. “Alkenyl” includes straight- or branched-chain alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the various butenyl, pentenyl and hexenyl isomers. “Alkenyl” also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. “Alkynyl” includes linear or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl, and the various butynyl, pentynyl and hexynyl isomers. “Alkynyl” can also include a moiety composed of a plurality of triple bonds such as 2,5-hexadiynyl. “Alkoxy” includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy, and the various butoxy, pentoxy and hexyloxy isomers. “Alkoxyalkyl” refers to an alkoxy substitution on an alkyl. Examples of “alkoxyalkyl” include CH ₃ OCH ₂ , CH ₃ OCH ₂ CH ₂ , CH ₃ CH ₂ OCH ₂ and CH ₃ CH ₂ OCH ₂ CH ₂ . “Alkenyloxy” includes straight-chain or branched alkenyloxy moieties. Examples of “alkenyloxy” include H ₂ C═CHCH ₂ O, (CH ₃ ) CH═CHCH ₂ O and CH ₂ ═CHCH ₂ CH ₂ O. “Alkynyloxy” includes straight-chain or branched alkynyloxy moieties. Examples of “alkynyloxy” include HC≡CCH ₂ O and CH ₃ C≡CCH ₂ O. “Alkylthio” includes methylthio, ethylthio, and branched or straight chain alkylthio moieties such as various propylthio and butylthio isomers. “Alkylsulfinyl” includes both enantiomers of an alkylsulfinyl group. Examples of “alkylsulfinyl” include CH ₃ S (O), CH ₃ CH ₂ S (O), CH ₃ CH ₂ CH ₂ S (O), (CH ₃ ) ₂ CHS (O) and various butylsulfinyls. Isomers. Examples of “alkylsulfonyl” include CH ₃ S (O) ₂ , CH ₃ CH ₂ S (O) ₂ , CH ₃ CH ₂ CH ₂ S (O) ₂ , (CH ₃ ) ₂ CHS (O) ₂ and Various butylsulfonyl isomers are mentioned. “Alkylamino”, “dialkylamino”, “alkenylthio”, “alkenylsulfinyl”, “alkenylsulfonyl”, “alkynylthio”, “alkynylsulfinyl”, “alkynylsulfonyl” and the like are defined as in the above examples. . “Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties attached to straight or branched chain alkyl groups. “Alkylcycloalkyl” refers to an alkyl substitution on a cycloalkyl moiety. Examples include 4-methylcyclohexyl and 3-ethylcyclopentyl. The term “aromatic heterocycle” includes fully aromatic heterocycles. Aromatic is when each ring atom is essentially in the same plane and has a p-orbital perpendicular to the ring plane, and (4n + 2) π electrons are where n is 0 or a positive integer Represents obeying the Hückel rule in relation to the ring. The term carbocyclic aromatic group is synonymous with the term monocyclic aromatic group. A wide variety of synthetic methods are known in the art for the preparation of aromatic heterocycles, see Comprehensive Heterocyclic Chemistry, Volume 8, A. R. Catricky (A.R. Katritzky) and C.I. W. Editor-in-Chief of C. W. Rees, Pergamon Press, Oxford, 1984, and Comprehensive Heterocyclic Chemistry II, Volume 12, A. R. Catricky, C.R. W. C. W. Rees and E.C. F. See EF Scriven, Editor-in-Chief, Pergamon Press, Oxford, 1996. The 5- and 6-membered aromatic heterocycles described with respect to R ⁷ typically comprise 1 to 4 heteroatom ring members, which contain 0 to 4 N, 0 Selected from ˜1 O and 0-1 S atoms. Presentation 1 shows an example of an aromatic heterocycle, and H-1 to H-55 are not intended to limit the aromatic heterocycle within the scope of the present invention, but are interpreted as examples.

[Where:
Each R ⁷¹ is independently R ⁴⁵ ;
R ^71a , R ⁷² and R ⁷³ are independently H or R ⁴⁵ ;
p is an integer from 0 to 3 and q is an integer from 0 to 2.]

References herein to R ⁷ groups H-1 to H-55 refer to those shown in Presentation 1.

Those skilled in the art recognize that not all nitrogen-containing heterocycles can form N-oxides because nitrogen requires a lone pair of electrons available for oxidation to oxides, and those capable of forming N-oxides. Those skilled in the art will recognize the nitrogen-containing heterocycles. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation of heterocyclic and tertiary amine N-oxides are well known to those skilled in the art and include peroxyacids such as peracetic acid and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, t-butylhydro Includes oxidation of heterocycles and tertiary amines with alkyl hydroperoxides such as peroxides, sodium perborate, and dioxiranes such as dimethyldioxirane. The methods for preparing these N-oxides are widely described and reviewed in the literature. For example, T.W. L. TL Gilchrist, Comprehensive Organic Synthesis, Vol. 7, pages 748-750, S.C. V. Edited by S. V. Ley, Pergamon Press (Pergamon)
Press); M. Tissler and B.C. B. Stanovnik, Comprehensive Heterocyclic Chemistry, Vol. 3, pp. 18-20. J. et al. A. B. Tolton and A. B. Edited by A. McKillop, Pergamon Press; R. GR Grimmett and B.M. R. T.A. B. R. T. Keene, Advances in Heterocyclic Chemistry, Vol. 43, pp. 149-161. R. Edited by A.R. Katritzky, Academic Press; M. Tissler and B.C. B. Stanovnik, Advances in Heterocyclic Chemistry, Vol. 9, pp. 285-291. R. Catricky and A.R. J. et al. Edited by AJ Boulton, Academic Press; W. H. Cheeseman and E.G. S. G. W. S. Welstiuk, Advances in Heterocyclic Chemistry, Vol. 22, 390-392, A.E. R. Catricky and A.R. J. et al. See AJ Boulton, Academic Press.

The term “halogen”, either alone or in combination with words such as “haloalkyl”, includes fluorine, chlorine, bromine or iodine. Furthermore, when used in a combined word such as “haloalkyl”, said alkyl may be partially or fully substituted by halogen atoms which may be the same or different. Examples of “haloalkyl” include F ₃ C, ClCH ₂ , CF ₃ CH ₂ and CF ₃ CCl ₂ . The terms “haloalkenyl”, “haloalkynyl”, “haloalkoxy”, “haloalkylthio” and the like are defined similarly to the term “haloalkyl”. Examples of “haloalkenyl” include (Cl) ₂ C═CHCH ₂ and CF ₃ CH ₂ CH═CHCH ₂ . Examples of “haloalkynyl” include HC≡CCHCl, CF ₃ C≡C, CCl ₃ C≡C and FCH ₂ C≡CCH ₂ . Examples of “haloalkoxy” include CF ₃ O, CCl ₃ CH ₂ O, HCF ₂ CH ₂ CH ₂ O, and CF ₃ CH ₂ O. Examples of “haloalkylthio” include CCl ₃ S, CF ₃ S, CCl ₃ CH ₂ S and ClCH ₂ CH ₂ CH ₂ S. Examples of “haloalkylsulfinyl” include CF ₃ S (O), CCl ₃ S (O), CF ₃ CH ₂ S (O) and CF ₃ CF ₂ S (O). Examples of “haloalkylsulfonyl” include CF ₃ S (O) ₂ , CCl ₃ S (O) ₂ , CF ₃ CH ₂ S (O) ₂ and CF ₃ CF ₂ S (O) ₂ .

The total number of carbon atoms in the substituent is represented by the prefix “C _i -C _j ”, where i and j are numbers from 1-14. For example, C ₁ -C ₃ alkylsulfonyl indicates methylsulfonyl to propylsulfonyl, C ₂ alkoxyalkyl indicates CH ₃ OCH ₂ , and C ₃ alkoxyalkyl indicates, for example, CH ₃ CH (OCH ₃ ), CH ₃ OCH ₂ CH ₂ or CH ₃ CH ₂ OCH ₂ represents and C ₄ alkoxyalkyl refers to various isomers of alkyl groups substituted by alkoxy groups containing a total of 4 carbon atoms, including CH ₃ CH ₂ CH ₂ OCH ₂ and CH ₃ CH ₂ OCH ₂ CH ₂ are mentioned. Examples of “alkylcarbonyl” include C (O) CH ₃ , C (O) CH ₂ CH ₂ CH ₃ and C (O) CH (CH ₃ ) ₂ . Examples of “alkoxycarbonyl” include CH ₃ OC (═O), CH ₃ CH ₂ OC (═O), CH ₃ CH ₂ CH ₂ OC (═O), (CH ₃ ) ₂ CHOC (═O) and various Butoxy- or pentoxycarbonyl isomers. In the above, when a compound of Formula I is composed of one or more heterocycles, all substituents are substituted by substituting hydrogen on said carbon or nitrogen through any available carbon or nitrogen. Bonded to these rings.

The compound is substituted with a substituent having a subscript indicating that the number of instances of the substituent (ie, the number of occurrences) can be changed (eg, (R ^d ) _1-3 ), or Previously, if there is a number range indicating that the number of instances of the substituent is variable (eg, 1-3 R ^d ), if the number of instances is greater than 1, each instance is a substituent. Independently selected from the group of groups defined for. Further, where the subscript represents a range, for example (R ^d ) _i−j , the illustrative number of substituents may be selected from an integer including all between i and j.

For example, with respect to R ¹⁵ or R ³⁴ , if a group contains a substituent that may be hydrogen, it is recognized that this substituent is taken as hydrogen, which is equivalent to said group that is unsubstituted.

  The compounds of the present invention can also exist as one or more stereoisomers. Various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will recognize that one stereoisomer may be more active and / or exhibit beneficial effects when enriched with respect to other stereoisomers or separated from other stereoisomers. will do. In addition, those skilled in the art know how to separate, concentrate and / or selectively produce said stereoisomers. The present invention therefore comprises compounds selected from formula I, their N-oxides and agriculturally suitable salts. The compounds of the invention may exist as mixtures of stereoisomers, as individual stereoisomers, or in optically active form.

A compound of formula I where R is CO ₂ H (ie, a carboxylic acid functional group) is considered to be a compound that binds to an active site on a plant enzyme or receptor to cause a herbicidal effect on the plant. Other compounds of formula I in which the substituent R is a group convertible to a carboxylic acid function (ie CO ₂ H) in the plant or environment provide similar herbicidal effects and are within the scope of the invention . Thus, a “herbicidally effective derivative of CO ₂ H” when used to describe the substituent R in Formula I is any salt, ester, carboxamide, acyl hydrazide, imidate, thioimidate, amidine, Acyl halides, acyl cyanides, acid anhydrides, ethers, acetals, orthoesters, carboxaldehydes, oximes, hydrazones, thioacids, thioesters, dithiol esters, nitriles, or compounds of formula I without herbicidal activity and plants Or in the art to provide a carboxylic acid functional group that is hydrolyzed, oxidized, reduced or otherwise metabolized in soil or metabolizable and is dissociable or non-dissociable depending on the pH. Defined as any other known carboxylic acid derivative.

Agriculturally suitable salts of the compounds of the present invention are such that the derived salt retains sufficient water solubility for bioavailability and thus herbicidal effectiveness, and the salt counterion for agricultural applications. As appropriate, salts formed by contact with acids or bases or through ion exchange. Agriculturally suitable salts of the compounds of the present invention include hydrobromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, salicylic acid, And acid addition salts with inorganic or organic acids such as tartaric acid, 4-toluenesulfonic acid or valeric acid. Agriculturally suitable salts of the compounds of the present invention also include those formed with strong bases (eg, sodium, potassium, lithium or quaternary ammonium hydroxides) or amines. Under environmental and physiological conditions, the salts of the compounds of the present invention are in equilibrium with their corresponding non-salt forms, indicating that agriculturally suitable salts share the biological utility of non-salt forms. Those skilled in the art will recognize.

Particularly useful are agriculturally suitable salts of compounds of formula I formed by a strong base or amine, wherein R is CO ₂ H, including those where R ² is CO ₂ H. As is well known in the art, by deprotonation caused by contact with the carboxylic acid group (CO 2 _H) with a base, carboxylate ions corresponding to (CO ^_2,) derived from and typically bases A counter ion with a positive charge is generated. Since most of the derived salts have sufficient water solubility for bioavailability, a wide range of counterions forms agriculturally suitable salts of compounds of formula I where R is CO ₂ H. Illustrative special mention is that the counter ion is an alkali metal cation such as lithium, sodium or potassium, a quaternary ammonium such as tetramethylammonium, a tertiary sulfonium such as trimethylsulfonium, or dimethylamine A salt of a compound of formula I derived from an amine such as diethanolamine (diolamine), triethanolamine (triolamine), wherein R is CO ₂ H.

Also particularly useful are the esters and thioester derivatives of CO ₂ H as R in the compounds of formula I. As is well known in the art, an ester group (ie, CO ₂ R ^AL ) is obtained from the condensation of a carboxylic acid functional group (CO ₂ H) with an alcohol (ie, R ^AL OH). Here, ^RAL is a group derived from an alcohol. A wide range of methods are known for producing such esters. Similarly, a thioester group of formula C (O) SR ^AL is conceptually regarded as a condensation product of a carboxylic acid functional group and a thioalcohol of formula R ^AL SH (often referred to as a mercaptan). Various methods are known for producing such thioesters. The compounds of formula I wherein R is CO ₂ H are herbicidal and their derivatized esters and thioesters are sensitive to hydrolysis (to R which is CO ₂ H), especially in the presence of hydrolases. Where the properties are high, compounds of formula I where R ¹ is an ester (ie, CO ₂ R ^AL ) or a thioester (ie, C (O) SR ^AL ) are generally useful as herbicides. Among the herbicidally effective derivatives of CO ₂ H, esters and thioester derivatives, particularly ester derivatives, are most conveniently prepared and useful. If the group R ^AL has two or more OH or SH functional groups, this group may be condensed with two or more of the pyrimidine ring systems of the formula I having CO ₂ H as R. When the derived multi-esterified derivative is hydrolyzed to a compound of formula I having CO ₂ H as R, the multi-esterified derivative is a herbicidally effective derivative of CO ₂ H. Illustrative noteworthy are CO ₂ H where R is methanol, ethanol, butanol, 2-butoxyethanol, 2-ethylhexanol, isopropanol, 2-methylpropanol (isobutanol), octanol isomers (isoctanol) and Ester and thioester compounds of formula I which are esterified with ethanethiol to form methyl, ethyl, butyl, 2-butoxyethyl, 2-ethylhexyl, isopropyl, 2-methylpropyl, isooctyl and ethylthioesters, respectively. Of note are methyl and ethyl esters.

Examples of embodiments of the present invention include the following.
Embodiment 1. FIG. A compound of formula I wherein j is 0.

  Embodiment 2. FIG. A compound of formula I wherein k is 0.

Embodiment 3. FIG. A compound of formula I wherein R ¹⁵ is H.

Embodiment 4 FIG. Embodiment 4. A compound of Embodiment 3 wherein R ¹⁶ is H.

Embodiment 5. FIG.
R is CO ₂ R ¹² , CH ₂ OR ¹³ , CH (OR ⁴⁶ ) (OR ⁴⁷ ), CHO, C (= NOR ¹⁴ ) H, C (= NNR ⁴⁸ R ⁴⁹ ) H, C (═O) N (R ¹⁸ ) R ¹⁹ , C (= S) OR ⁵⁰ , C (= O) SR ⁵¹ , C (= S) SR ⁵² or C (= NR ⁵³ ) YR ⁵⁴ ,
R ¹² is H, —CH— [C (O) O (CH ₂ ) _m ] —, —N═C (R ⁵⁵ ) R ⁵⁶ ; or C _{1 to} C ₁₄ alkyl, C _{3 to} C ₁₂ cycloalkyl, C ₄ -C _{12 alkylcycloalkyl,} C 4 _{-C 12 cycloalkylalkyl,} a C 2 _{-C 14 alkenyl,} C 2 _{-C 14} group selected from an alkynyl and phenyl, one to three optionally each group May be substituted by R ²⁷ , or R ¹² may be a divalent group linking the respective carboxylate ester functional groups CO ₂ R ¹² of the two pyrimidine ring systems of formula I, The group is selected from —CH ₂ —, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ — and —CH (CH ₃ ) CH ₂ —;
R ¹³ is H, C ₁ -C ₁₀ alkyl optionally substituted by 1 to 3 R ²⁸ , or benzyl;
R ¹⁴ is H, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or benzyl;
R ¹⁸ is H, C ₁ -C ₄ alkyl, hydroxy, C ₁ -C ₄ alkoxy or S (O) ₂ R ⁵⁷ ,
R ¹⁹ is H or C ₁ -C ₄ alkyl;
Each R ²⁷ is independently halogen, cyano, hydroxycarbonyl, C ₂ -C ₄ alkoxycarbonyl, hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, _amino, C 1 -C _{4 alkylamino,} C 2 -C _{4 dialkylamino, -CH- [O (CH 2)} n] - or optionally be substituted by one to three ^{R 44} Is good phenyl, or two R ²⁷ together are —OC (O) O— or —O (C (R ⁵⁸ ) (R ⁵⁸ )) _1-2 O—, or two R ²⁷ in the above form an oxygen atom, together with the carbon atom to which they are bonded, form a carbonyl moiety,
Each R ²⁸ is independently halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, amino, C ₁ -C ₄ alkylamino or C _{2 to} C ₄ dialkylamino, or two R ²⁸ as oxygen atoms together with the carbon atom to which they are attached to form a carbonyl moiety;
Each R ⁴⁴ is independently halogen, C ₁ -C ₄ alkyl, C ₁ -C ₃ haloalkyl, hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₃ haloalkoxy, C ₁ -C ₃ alkylthio, C _1- C ₃ haloalkylthio, amino, C ₁ -C ₃ alkylamino, C ₂ -C ₄ dialkylamino or nitro;
R ⁴⁶ and R ⁴⁷ are independently C ₁ -C ₄ alkyl or C ₁ -C ₃ haloalkyl, or R ⁴⁶ and R ^{47 taken} together are —CH ₂ CH ₂ —, —CH ₂ CH (CH ₃₎ - or - _{(CH 2) 3} - it is and,
R ⁴⁸ is H, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkylcarbonyl, C ₂ -C ₄ alkoxycarbonyl or benzyl,
R ⁴⁹ is H, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl,
R ⁵⁰ , R ⁵¹ and R ⁵² are H; or C ₁ -C ₁₄ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₄ -C ₁₂ alkyl cycloalkyl, C ₄ -C ₁₂ cycloalkylalkyl, C ₂ -C ₁₄ A group selected from alkenyl and C ₂ -C ₁₄ alkynyl, each group optionally substituted by 1 to 3 R ²⁷ ,
Y is O, S or NR ⁶¹ ;
R ⁵³ is H, C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, C ₂ -C ₄ alkoxyalkyl, OH or C ₁ -C ₃ alkoxy;
R ⁵⁴ is C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl or C ₂ -C ₄ alkoxyalkyl, or R ⁵³ and R ^{54 taken} together — (CH ₂ ) ₂ —, —CH ₂ CH (CH ₃ ) — or — (CH ₂ ) ₃ —,
R ⁵⁵ and R ⁵⁶ are independently C ₁ -C ₄ alkyl;
R ⁵⁷ is C ₁ -C ₄ alkyl, C ₁ -C ₃ haloalkyl or NR ⁵⁹ R ⁶⁰ ;
Each R ⁵⁸ is independently selected from H and C ₁ -C ₄ alkyl;
R ⁵⁹ and R ⁶⁰ are independently H or C ₁ -C ₄ alkyl;
R ⁶¹ is H, C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl or C ₂ -C ₄ alkoxyalkyl;
A compound of formula I wherein m is an integer from 2 to 3 and n is an integer from 1 to 4.

Embodiment 6. FIG. A compound of Formula I wherein R ² is other than alkoxyalkyl or alkylthioalkyl when R ¹ is optionally substituted cyclopropyl.

Embodiment 7. FIG. A compound of Formula I wherein R ² is other than alkoxyalkyl or alkylthioalkyl.

Embodiment 8. FIG.
R ² is CO ₂ R ¹² , CH ₂ OR ¹³ , CH (OR ⁴⁶ ) (OR ⁴⁷ ), CHO, C (= NOR ¹⁴ ) H, C (= NNR ⁴⁸ R ⁴⁹ ) H, (O) _j C (R ¹⁵ ) (R ¹⁶ ) CO ₂ R ¹⁷ , C (= O) N (R ¹⁸ ) R ¹⁹ , C (= S) OR ⁵⁰ , C (= O) SR ⁵¹ , C (= S) SR ⁵² or C ( = NR ⁵³ ) YR ⁵⁴ ,
R ¹⁷ is C ₁ -C ₁₀ alkyl optionally substituted by 1 to 3 R ²⁹ , or benzyl, and each R ²⁹ is independently halogen, C ₁ -C ₄ alkoxy, C ₁ -C _{4 haloalkoxy,} C 1 -C _{4 alkylthio,} C 1 -C ₄ haloalkylthio, _amino, C 1 -C ₄ alkylamino or _C 2 -C ₄ a compound of embodiment 5 dialkylamino.

Embodiment 9. FIG. The compound of Embodiment 8 wherein when R ² is CH ₂ OR ¹³ , R ¹³ is other than alkyl.

Embodiment 10 FIG. The compound of Embodiment 8 wherein when R ² is CH ₂ OR ¹³ , R ¹³ is other than optionally substituted alkyl.

Embodiment 11. FIG. Embodiment 9. A compound of Embodiment 8 wherein R ² is other than CH ₂ OR ¹³ .

  Embodiment 12 FIG. Embodiment 9. A compound of Embodiment 8 wherein j is 0.

Embodiment 13. FIG. Embodiment 12. A compound of Embodiment 12 wherein R ² is CO ₂ R ¹² , CH ₂ OR ¹³ , CHO or CH ₂ CO ₂ R ¹⁷ .

Embodiment 14 FIG. Embodiment 14. A compound of Embodiment 13 wherein R ² is CO ₂ R ¹² .

Embodiment 15. FIG. Embodiment 15. A compound of Embodiment 14 wherein R ¹² is H, C ₁ -C ₈ alkyl or C ₁ alkyl substituted by phenyl optionally substituted by 1 to 3 R ⁴⁴ .

Embodiment 16. FIG. Embodiment 16. A compound of Embodiment 15 wherein R ¹² is H, C ₁ -C ₄ alkyl or C ₁ alkyl substituted by phenyl optionally substituted by 1 to 3 R ⁴⁴ .

Embodiment 17. FIG. Embodiment 16. A compound of Embodiment 16 wherein R ¹² is H, C ₁ -C ₄ alkyl or benzyl.

Embodiment 18. FIG. A compound of formula I wherein R ² is CO ₂ H, their agriculturally suitable salts or ester or thioester derivatives.

Embodiment 19. FIG. Embodiment 19. A compound of Embodiment 18 wherein R ² is CO ₂ H, an agriculturally suitable salt or ester derivative thereof.

Embodiment 20. FIG. A compound of Formula I wherein R ¹ is cyclopropyl optionally substituted with 1 to 5 R ⁵ .

Embodiment 21. FIG. A compound of Formula I wherein R ¹ is isopropyl optionally substituted with 1 to 5 R ⁶ .

Embodiment 22. FIG. A compound of formula I wherein R ¹ is phenyl optionally substituted by 1 to 3 R ⁷ .

Embodiment 23. FIG. Compounds of formula I are good isopropyl optionally substituted by 1-5 R ⁶ optionally may cyclopropyl or optionally substituted by 1-5 R ⁵ optionally R ¹ is.

Embodiment 24. FIG. A compound of formula I wherein R ¹ is cyclopropyl optionally substituted with 1 to 5 R ⁵ or phenyl optionally substituted with 1 to 3 R ⁷ .

Embodiment 25. FIG. A compound of Formula I wherein R ¹ is isopropyl optionally substituted with 1 to 5 R ⁶ or phenyl optionally substituted with 1 to 3 R ⁷ .

Embodiment 26. FIG. A compound of Formula I wherein R ¹ is other than cyclopropyl.

Embodiment 27. FIG. A compound of Formula I wherein R ¹ is cyclopropyl optionally substituted with 1 to 2 R ⁶ or phenyl optionally substituted with 1 to 3 R ⁷ .

Embodiment 28. FIG. Embodiment 27. A compound of Embodiment 27 wherein R ¹ is cyclopropyl optionally substituted with 1 to 2 R ⁶ .

Embodiment 29. FIG. Embodiment 27. A compound of Embodiment 27 wherein R ¹ is cyclopropyl or phenyl optionally substituted by 1 to 3 R ⁷ .

Embodiment 30. FIG. Embodiment 28. A compound of Embodiment 28 wherein R < ¹ > is cyclopropyl.

Embodiment 31. FIG. Embodiment 27. A compound of Embodiment 27 wherein R ¹ is phenyl optionally substituted by 1 to 3 R ⁷ .

Embodiment 32. FIG. R ¹ is replaced by the group R ⁷ in the cyclopropyl or para-position, and optionally the compound of embodiment 27 is phenyl substituted by 1-2 R ⁷ in the other position.

Embodiment 33. FIG. Embodiment 33 wherein R ¹ is phenyl substituted at the cyclopropyl or para position by a halogen, methyl or methoxy group and optionally substituted at other positions by one or two groups selected from halogen and methyl. Compound.

Embodiment 34. FIG. Embodiment 34. A compound of Embodiment 33 wherein R ¹ is phenyl substituted with a halogen group at the cyclopropyl or para position and optionally substituted at other positions with one or two groups selected from halogen and methyl.

Embodiment 35. FIG. Embodiment 35. A compound of Embodiment 34 wherein R ¹ is phenyl substituted at the cyclopropyl or para position by a Br or Cl group and optionally substituted at other positions by 1 to 2 groups selected from halogen and methyl.

Embodiment 36. FIG. Embodiment 35. A compound of Embodiment 35 wherein R ¹ is phenyl substituted at the para position by a Br or Cl group and optionally substituted at other positions by 1 to 2 groups selected from halogen and methyl.

Embodiment 37. FIG. Embodiment 36. A compound of Embodiment 35 wherein R ¹ is cyclopropyl or phenyl substituted by a Br or Cl group at the para position.

Embodiment 38. FIG. Embodiment 38. A compound of Embodiment 37 wherein R ¹ is phenyl substituted at the para position by a Br or Cl group.

Embodiment 39. FIG. A compound of Formula I wherein R ⁷ is other than cyano.

Embodiment 40. FIG. A compound of formula I wherein R ⁷ is selected from other than optionally substituted phenyl, phenoxy and 5- and 6-membered aromatic heterocycles.

Embodiment 41. FIG. Each R ⁷ is independently selected from halogen, C ₁ -C ₂ alkyl, C ₁ -C ₂ haloalkyl, C ₁ -C ₂ alkoxy or C ₁ -C ₂ haloalkoxy, or two adjacent R's ⁷ together —OCH ₂ O—, —CH ₂ CH ₂ O—, —OCH (CH ₃ ) O—, —OC (CH ₃ ) ₂ O—, —OCF ₂ O—, —CF ₂ CF _{2 O -, - OCF 2 CF 2} O- or -CH = CH-CH = CH- the compound of formula I wherein.

Embodiment 42. FIG. Each R ⁷ is independently selected from halogen, C ₁ -C ₂ alkyl, C ₁ -C ₂ haloalkyl, C ₁ -C ₂ alkoxy or C ₁ -C ₂ haloalkoxy, or two adjacent R's 42. The compound of Embodiment 41, wherein ⁷ together are —OCH ₂ O—, —CH ₂ CH ₂ O—, —OCH (CH ₃ ) O—, or —OCF ₂ O—.

Embodiment 43. FIG. Embodiment 43. A compound of Embodiment 42 wherein each R ⁷ is independently selected from halogen, C ₁ -C ₂ alkyl, C ₁ fluoroalkyl, C ₁ -C ₂ alkoxy, or C ₁ fluoroalkoxy.

Embodiment 44. FIG. A compound of formula I wherein each R ⁷ is independently selected from halogen, methyl and methoxy.

Embodiment 45. FIG. Embodiment 45. A compound of Embodiment 44 wherein each R ⁷ is independently selected from halogen and methyl.

Embodiment 46. FIG. Embodiment 46. A compound of Embodiment 45 wherein each R ⁷ is independently selected from F, Cl and Br.

Embodiment 47. Embodiment 46. A compound of Embodiment 46 wherein each R ⁷ is independently selected from Cl and Br.

Embodiment 48. FIG. A compound of Formula I wherein R ³ is other than cyano.

Embodiment 49. A compound of Formula I wherein R ³ is other than nitro.

Embodiment 50. FIG. A compound of formula I wherein R ³ is halogen, nitro, OR ²⁰ , SR ²¹ or N (R ²² ) R ²³ .

Embodiment 51. FIG. Embodiment 50. A compound of Embodiment 50 wherein R ³ is halogen.

Embodiment 52. FIG. Embodiment 52. A compound of Embodiment 51 wherein R ³ is Br or Cl.

Embodiment 53. FIG. Embodiment 53. A compound of Embodiment 52 wherein R ³ is Cl.

Embodiment 54. FIG. A compound of Formula I wherein R ⁴ is —N (R ²⁴ ) R ²⁵ .

Embodiment 55. FIG. A compound of Formula I wherein R ²⁴ is other than C ₂ -C ₄ alkynyl optionally substituted by 1 to 2 R ³² .

Embodiment 56. FIG. R ²⁴ is H, C (O) R ³³ or C ₁ -C ₄ alkyl optionally substituted by R ³⁰ and R ²⁵ is H or C ₁ -C ₂ alkyl, or R ²⁴ And R ^{25 taken} together = C (R ³⁹ ) N (R ⁴⁰ ) R ⁴¹

Embodiment 57. FIG. Embodiment 56. wherein R ²⁴ is H, C (O) CH ₃ or C ₁ -C ₄ alkyl optionally substituted by R ³⁰ and R ²⁵ is H or C ₁ -C ₂ alkyl. Compound.

Embodiment 58. FIG. Embodiment 58. A compound of Embodiment 57 wherein R ²⁴ and R ²⁵ are independently H or methyl.

Embodiment 59. FIG. Embodiment 58. A compound of Embodiment 58 wherein R ²⁴ and R ²⁵ are H.

Embodiment 60. FIG. A compound of formula I wherein R ³⁰ is halogen, methoxy, C ₁ fluoroalkoxy, methylthio, C ₁ fluoroalkylthio, amino, methylamino, dimethylamino or methoxycarbonyl.

Embodiment 61. FIG. A compound of Formula I wherein R ³³ is H or C ₁ -C ₃ alkyl.

Embodiment 62. FIG. Embodiment 62. A compound of Embodiment 61 wherein R ³³ is CH ₃ .

Embodiment 63. FIG. A compound of Formula I wherein R ³⁹ is H or C ₁ -C ₂ alkyl.

Embodiment 64. FIG. A compound of Formula I wherein R ⁴⁰ and R ⁴¹ are independently H or C ₁ -C ₂ alkyl.

Embodiment 65. FIG. A compound of Formula I wherein R ³ is other than OH.

Embodiment 66. FIG. A compound of Formula I wherein R ³ is other than OR ²⁰ .

Embodiment 67. FIG. A compound of formula I wherein R ²⁴ and R ²⁵ are each H when j is 1 and R ¹ is isopropyl substituted by R ⁶ which is at least one halogen.

Embodiment 68. FIG. A compound of formula I wherein R ²⁴ and R ²⁵ are each H when j is 1 and R ¹ is optionally substituted isopropyl.

Embodiment 69. A compound of Formula I wherein when j is 1, R ²⁴ and R ²⁵ are each H.

Embodiment 70. FIG. A compound of Formula I wherein when j is 1, R ⁶ is other than halogen.

Embodiment 71. FIG. A compound of Formula I wherein when j is 1, R ¹ is other than optionally substituted isopropyl.

Embodiment 72. FIG. When j is 1, R ¹ is cyclopropyl, isopropyl optionally substituted by 1 to 5 R ⁵ , or phenyl optionally substituted by 1 to 3 R ⁷ A compound of formula I.

Embodiment 73. FIG. A compound of Formula I wherein when j is 1, R ¹ is cyclopropyl, isopropyl, or phenyl optionally substituted by 1 to 3 R ⁷ .

Embodiment 74. FIG. A compound of Formula I wherein R is other than cyano when R ¹ is phenyl optionally substituted by 1 to 3 R ⁷ .

  Embodiment 75. FIG. A compound of formula I wherein R is other than cyano.

Embodiment 76. The compound of Embodiment 5 wherein R is CO ₂ R ¹² when R ¹ is phenyl optionally substituted by 1 to 3 R ⁷ .

Embodiment 77. Embodiment 6. A compound of Embodiment 5 wherein R is CO ₂ R ¹² .

Embodiment 78. The compound of Embodiment 8 wherein R ² is CO ₂ R ¹² when R ¹ is phenyl optionally substituted with 1 to 3 R ⁷ .

Embodiment 79. Embodiment 9. A compound of Embodiment 8 wherein R ² is CO ₂ R ¹² .

Embodiment 80. FIG. When R ¹ is phenyl optionally substituted by 1 to 3 R ⁷ , R ²⁴ is H, C (═O) R ³³ , nitro, OR ³⁴ , S (O) ₂ R ³⁵ or A compound of Formula I wherein N (R ³⁶ ) R ³⁷ and R ²⁵ is H or C (═O) R ³³ .

Embodiment 81. FIG. A compound of formula I wherein R ²⁴ and R ²⁵ are each H when R ¹ is phenyl optionally substituted by 1 to 3 R ⁷ .

Embodiment 82. R ²⁴ is H, C (═O) R ³³ , nitro, OR ³⁴ , S (O) ₂ R ³⁵ or N (R ³⁶ ) R ³⁷ and R ²⁵ is H or C (═O) R ³³ A compound of formula I.

Embodiment 83. FIG. A compound of Formula I wherein R ²⁴ and R ²⁵ are each H.

Embodiment 84. When R ¹ is cyclopropyl or isopropyl optionally substituted by 1 to 5 R ⁶ , R is C (═W ¹ ) N (R ^b1 ) S (O) ₂ -R ^cd [Formula Wherein W comprises at least one atom, R ^b1 comprises at least one atom, and R ^cd comprises at least one atom].

Embodiment 85. FIG. If when R ¹ is a is a good isopropyl optionally substituted by 1-5 R ⁶ optionally may cyclopropyl or optionally substituted by 1-5 R ^5, R is C (= W ¹ ) N (R ^b1 ) S (O) ₂ -R ^{cd wherein} W comprises at least one atom, R ^b1 comprises at least one atom and R ^cd comprises at least one atom. A compound of formula I which is other than

Embodiment 86. R is other than C (= W ¹ ) N (R ^b1 ) S (O) ₂ —R ^cd [wherein W comprises at least one atom and R ^b1 comprises at least one atom. And R ^cd comprises at least one atom].

Embodiment 87. FIG. Embodiment 6. A compound of Embodiment 5 wherein R ¹⁸ is H, C ₁ -C ₄ alkyl, hydroxy or C ₁ -C ₄ alkoxy.

Embodiment 88. FIG. Embodiment 9. A compound of Embodiment 8 wherein R ¹⁸ is H, C ₁ -C ₄ alkyl, hydroxy or C ₁ -C ₄ alkoxy.

Embodiment 89. A compound of formula I wherein each R ⁵ and R ⁶ is independently halogen, C ₁ -C ₂ alkyl or C ₁ -C ₂ haloalkyl.

Embodiment 90. FIG. A compound of formula I wherein R ¹⁵ is H, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, hydroxy, C ₁ -C ₄ alkoxy or C ₂ -C ₄ alkylcarbonyloxy.

Embodiment 91. FIG. A compound of formula I wherein R ¹⁶ is H, halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl.

Embodiment 92. FIG. R ²⁴ is H, C ₁ -C ₄ alkyl optionally substituted by 1 to 2 R ³⁰ , C ₂ -C ₄ alkenyl optionally substituted by 1 to 2 R ³¹ Or C ₂ -C ₄ alkynyl optionally substituted by 1 to 2 R ³² , or R ²⁴ is C (═O) R ³³ , nitro, OR ³⁴ ,
A compound of formula I which is S (O) ₂ R ³⁵ or N (R ³⁶ ) R ³⁷ .

Embodiment 93. A compound of formula I wherein each R ³³ is independently H, C ₁ -C ₄ alkyl, C ₁ -C ₃ haloalkyl, C ₁ -C ₄ alkoxy, phenoxy or benzyloxy.

Embodiment 94. FIG. A compound of formula I wherein R ³⁴ is H, C ₁ -C ₄ alkyl or C ₁ -C ₃ haloalkyl.

Embodiment 95. A compound of Formula I wherein R ³⁶ is H or C ₁ -C ₄ alkyl.

Embodiment 96. R ¹² is H or C ₁ -C ₁₄ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₄ -C ₁₂ alkyl cycloalkyl, C ₄ -C ₁₂ cycloalkyl alkyl, C ₂ -C ₁₄ alkenyl and C Embodiment 5 wherein the group is selected from _{2 to} C ₁₄ alkynyl and is optionally substituted by 1 to 3 R ²⁷ , or —N═C (R ⁵⁵ ) R ⁵⁶ Compound.

Embodiment 97. FIG. Each R ²⁷ is independently halogen, hydroxycarbonyl, C ₂ -C ₄ alkoxycarbonyl, hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ halo alkylthio, _amino, C 1 -C _{4 alkylamino,} C 2 -C _{4 dialkylamino, -CH- [O (CH 2)} n] - or optionally substituted by one to three ^{R 44} phenyl Or two R ^{27 taken} together are —OC (O) O— or —O (C (R ⁵⁸ ) (R ⁵⁸ )) _1-2 O—, or two R Embodiment 6. A compound of Embodiment 5 wherein ²⁷ is an oxygen atom and together with the carbon atom to which they are attached, forms a carbonyl moiety.

Embodiment 98. FIG. Embodiment 6. A compound of Embodiment 5 wherein R ⁵³ is H, C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl or C ₂ -C ₄ alkoxyalkyl.

  The combination of Embodiments 1-98 is described by the following.

Embodiment A.
R ² is CO ₂ R ¹² , CH ₂ OR ¹³ , CH (OR ⁴⁶ ) (OR ⁴⁷ ), CHO, C (= NOR ¹⁴ ) H, C (= NNR ⁴⁸ R ⁴⁹ ) H, (O) _j C (R ¹⁵ ) (R ¹⁶ ) CO ₂ R ¹⁷ , C (= O) N (R ¹⁸ ) R ¹⁹ , C (= S) OR ⁵⁰ , C (= O) SR ⁵¹ , C (= S) SR ⁵² or C ( = NR ⁵³ ) YR ⁵⁴ ,
R ¹² is H, —CH— [C (O) O (CH ₂ ) _m ] —, —N═C (R ⁵⁵ ) R ⁵⁶ ; or C _{1 to} C ₁₄ alkyl, C _{3 to} C ₁₂ cycloalkyl, C ₄ -C _{12 alkylcycloalkyl,} C 4 _{-C 12 cycloalkylalkyl,} a C 2 _{-C 14 alkenyl,} C 2 _{-C 14} group selected from an alkynyl and phenyl, one to three optionally each group May be substituted by R ²⁷ , or R ¹² may be a divalent group linking the respective carboxylate ester functional groups CO ₂ R ¹² of the two pyrimidine ring systems of formula I, The group is selected from —CH ₂ —, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ — and —CH (CH ₃ ) CH ₂ —;
R ¹³ is H, C ₁ -C ₁₀ alkyl optionally substituted by 1 to 3 R ²⁸ , or benzyl;
R ¹⁴ is H, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or benzyl;
R ¹⁷ is C ₁ -C ₁₀ alkyl optionally substituted by 1 to 3 R ²⁹ , or benzyl;
R ¹⁸ is H, C ₁ -C ₄ alkyl, hydroxy, C ₁ -C ₄ alkoxy or S (O) ₂ R ⁵⁷ ,
R ¹⁹ is H or C ₁ -C ₄ alkyl;
Each R ²⁷ is independently halogen, cyano, hydroxycarbonyl, C ₂ -C ₄ alkoxycarbonyl, hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, _amino, C 1 -C _{4 alkylamino,} C 2 -C _{4 dialkylamino, -CH- [O (CH 2)} n] - or optionally be substituted by one to three ^{R 44} Is good phenyl, or two R ²⁷ together are —OC (O) O— or —O (C (R ⁵⁸ ) (R ⁵⁸ )) _1-2 O—, or two R ²⁷ in the above form an oxygen atom, together with the carbon atom to which they are bonded, form a carbonyl moiety,
Each R ²⁸ is independently halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, amino, C ₁ -C ₄ alkylamino or C _{2 to} C ₄ dialkylamino, or two R ²⁸ as oxygen atoms together with the carbon atom to which they are attached to form a carbonyl moiety;
Each R ²⁹ is independently halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, amino, C ₁ -C ₄ alkylamino or C a ₂ -C ₄ dialkylamino,
Each R ⁴⁴ is independently halogen, C ₁ -C ₄ alkyl, C ₁ -C ₃ haloalkyl, hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₃ haloalkoxy, C ₁ -C ₃ alkylthio, C _1- C ₃ haloalkylthio, amino, C ₁ -C ₃ alkylamino, C ₂ -C ₄ dialkylamino or nitro;
R ⁴⁶ and R ⁴⁷ are independently C ₁ -C ₄ alkyl or C ₁ -C ₃ haloalkyl, or R ⁴⁶ and R ^{47 taken} together are —CH ₂ CH ₂ —, —CH ₂ CH (CH ₃₎ - or - _{(CH 2) 3} - it is and,
R ⁴⁸ is H, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkylcarbonyl, C ₂ -C ₄ alkoxycarbonyl or benzyl,
R ⁴⁹ is H, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl,
R ⁵⁰ , R ⁵¹ and R ⁵² are H; or C ₁ -C ₁₄ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₄ -C ₁₂ alkyl cycloalkyl, C ₄ -C ₁₂ cycloalkylalkyl, C ₂ -C ₁₄ A group selected from alkenyl and C ₂ -C ₁₄ alkynyl, each group optionally substituted by 1 to 3 R ²⁷ ,
Y is O, S or NR ⁶¹ ;
R ⁵³ is H, C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, C ₂ -C ₄ alkoxyalkyl, OH or C ₁ -C ₃ alkoxy;
R ⁵⁴ is C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl or C ₂ -C ₄ alkoxyalkyl, or R ⁵³ and R ^{54 taken} together — (CH ₂ ) ₂ —, —CH ₂ CH (CH ₃ ) — or — (CH ₂ ) ₃ —,
R ⁵⁵ and R ⁵⁶ are independently C ₁ -C ₄ alkyl;
R ⁵⁷ is C ₁ -C ₄ alkyl, C ₁ -C ₃ haloalkyl or NR ⁵⁹ R ⁶⁰ ;
Each R ⁵⁸ is independently selected from H and C ₁ -C ₄ alkyl;
R ⁵⁹ and R ⁶⁰ are independently H or C ₁ -C ₄ alkyl;
R ⁶¹ is H, C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl or C ₂ -C ₄ alkoxyalkyl,
A compound of formula I wherein m is an integer from 2 to 3 and n is an integer from 1 to 4.

Embodiment B. A compound of Embodiment A wherein R ³ is halogen.

Embodiment C. R ¹ is cyclopropyl or phenyl substituted by a halogen, methyl or methoxy group at the para position and optionally substituted at other positions by one or two groups selected from halogen and methyl; and R ⁴ A compound of Embodiment B wherein is —N (R ²⁴ ) R ²⁵ .

Embodiment D. R ² is _{^{CO 2 R 12, CH 2 OR}} 13, CHO or A compound of Embodiment C is a _CH 2 _CO 2 ^{R 17.}

Embodiment E. R ²⁴ is H, C (O) R ³³ or C ₁ -C ₄ alkyl optionally substituted by R ³⁰ and R ²⁵ is H or C ₁ -C ₂ alkyl, or R ²⁴ And R ^{25 taken} together = C (R ³⁹ ) N (R ⁴⁰ ) R ⁴¹ .

Embodiment F. The compound of Embodiment E wherein R ² is CO ₂ R ¹² and R ²⁴ and R ²⁵ are H.

Embodiment G. A compound of Embodiment F wherein R ¹² is H, C ₁ -C ₄ alkyl or benzyl.

As a specific embodiment,
Methyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate,
Ethyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate,
Phenylmethyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate,
6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylic acid monosodium salt,
Methyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate,
Phenylmethyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate,
6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid monosodium salt,
Ethyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate,
Methyl 6-amino-5-chloro-2- (4-chlorophenyl) -4-pyrimidinecarboxylate;
Ethyl 6-amino-5-chloro-2- (4-chlorophenyl) -4-pyrimidinecarboxylate,
6-amino-5-chloro-2- (4-chlorophenyl) -4-pyrimidinecarboxylic acid,
Ethyl 6-amino-2- (4-bromophenyl) -5-chloro-4-pyrimidinecarboxylate,
The group consisting of methyl 6-amino-2- (4-bromophenyl) -5-chloro-4-pyrimidinecarboxylate and 6-amino-2- (4-bromophenyl) -5-chloro-4-pyrimidinecarboxylic acid And compounds of formula I selected from:

  A herbicidal composition of the present invention comprising a compound of the above embodiment is also a notable embodiment.

The present invention also relates to a method for controlling undesirable vegetation comprising applying a herbicidally effective amount of a compound of the present invention (eg, as a composition described herein) to a vegetation location. Also related. Of note as embodiments relating to methods of use are those involving the compounds of the above embodiments.

Of note, R ² is CO ₂ R ¹² , CH ₂ OR ¹³ , CHO, C (= NOR ¹⁴ ) H, C (R ¹⁵ ) (R ¹⁶ ) CO ₂ R ¹⁷ or C (═O) N (R ¹⁸⁾ and ^{R 19,} halogen each ^{R 7} is _{independently,} C 1 -C _{4 alkyl,} C 1 -C _{3 haloalkyl,} C 1 -C _{3 alkoxy,} C 1 -C _{3 haloalkoxy,} C 1 -C ₃ Alkylthio or C ₁ -C ₃ haloalkylthio and R ¹² is H, or C ₁ -C ₁₄ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₄ -C ₁₂ alkyl cycloalkyl, C ₄ -C ₁₂ A group selected from cycloalkylalkyl, C ₂ -C ₁₄ alkenyl and C ₂ -C ₁₄ alkynyl, each group optionally substituted by 1 to 3 R ²⁷ , R ^{1 3} is H, C ₁ -C ₁₀ alkyl or benzyl optionally substituted by 1 to 3 R ²⁸ , and R ¹⁴ is H, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl R ¹⁵ and R ¹⁶ are independently H, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, hydroxy or C ₁ -C ₄ alkoxy, and R ¹⁷ is optionally 1-3 C ₁ -C ₁₀ alkyl or benzyl optionally substituted by R ²⁹ , R ¹⁸ and R ¹⁹ are independently H or C ₁ -C ₄ alkyl, and each R ²⁷ is independently halogen, hydroxy _carbonyl, C 2 -C ₄ alkoxycarbonyl, _hydroxy, C 1 -C _{4 alkoxy,} C 1 -C _{4 haloalkoxy,} C 1 -C ₄ alkylthio, _{C 1} -C ₄ haloalkylthio, _amino, C 1 -C _{4 alkylamino,} C 2 -C _{4 dialkylamino, -CH- [O (CH 2)} n] - or optionally substituted by one to three ^{R 44} Or two R ²⁷ together with the carbon atom to which they are attached form a carbonyl moiety, each R ²⁸ and R ²⁹ is independently halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, amino, C ₁ -C ₄ alkylamino or C ₂ -C ₄ dialkylamino, each R ³⁰ , halogen R ³¹ and ^{R 32} are independently _hydroxy, C 1 -C _{4 alkoxy,} C 1 -C _{4 haloalkoxy,} C 1 -C _{4 alkylthio,} C 1 -C Haloalkylthio, _amino, C 1 -C _{4 alkylamino,} C 2 -C ₄ dialkylamino or _C 2 -C ₄ alkoxycarbonyl, halogen each ^{R 38} is _{independently,} C 1 -C _{3 alkyl, C} 1 ~ C _{3 alkoxy,} C 1 -C _{3 haloalkoxy,} C 1 -C _{3 alkylthio,} C 1 -C ₃ haloalkylthio, _amino, C 1 -C _{3 alkylamino,} C 2 -C ₄ dialkylamino or _C 2 -C ₄ Each of R ⁴⁴ is independently halogen, C ₁ -C ₄ alkyl, C ₁ -C ₃ haloalkyl, hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₃ haloalkoxy, C ₁ -C _{4 alkylthio,} C 1 -C ₃ haloalkylthio, _amino, C 1 -C _{3 alkylamino,} C 2 -C ₄ dialkylamino or two The compounds of formula I, including all geometric isomers and stereoisomers thereof, their N-oxides or agriculturally, wherein m is an integer from 2 to 5 and n is an integer from 1 to 4 Suitable salts, agricultural compositions containing them as well as their use as herbicides. Each R ⁵ and R ⁶ is independently halogen, C ₁ -C ₂ alkyl or C ₁ -C ₂ haloalkyl, and R ¹⁵ is H, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, hydroxy C ₁ -C ₄ alkoxy or C ₂ -C ₄ alkylcarbonyloxy, R ¹⁶ is H, halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl, R ²⁴ is H, optionally 1 C ₁ -C ₄ alkyl optionally substituted by 2 R ³⁰ , C ₂ -C ₄ alkenyl optionally substituted by 1 to 2 R ³¹ , or optionally 1-2 C ₂ -C ₄ alkynyl optionally substituted by R ³² or R ²⁴ is C (═O) R ³³ , nitro, OR ³⁴ , S (O) ₂ R ³⁵ Or N (R ³⁶ ) R ³⁷ where each R ³³ is independently H, C ₁ -C ₄ alkyl, C ₁ -C ₃ haloalkyl, C ₁ -C ₄ alkoxy, phenoxy or benzyloxy; Compounds of formula I, including all geometric and stereoisomers, wherein ³⁴ is H, C ₁ -C ₄ alkyl, C ₁ -C ₃ haloalkyl, and R ³⁶ is H or C ₁ -C ₄ alkyl Also noteworthy are their N-oxides or agriculturally suitable salts, agricultural compositions containing them, and their use as herbicides.

Compounds of formula I can be made by one or more of the following methods and variations described in Schemes 1-7 and accompanying text. The following compounds of formula I~12 of ^{R, R 1, R 2,} R 3, R 4, R 5, R 6, R 7, R 12, R 13, R 14, R 15, R 16, R 17 , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ^{35, R 36, R 37,} R 38, R 39, R 40, R 41, R 42, R 43, R 44, R 45, R 46, R 47, R 48, R 49, R 50, R 51, The definitions of R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , Y, j, k and n are As defined above in the description of the embodiments.

  As outlined in Scheme 1, compounds of Formula I can be prepared from chlorides of Formula 2 by reaction with an amine of Formula 3 optionally in the presence of a base such as triethylamine or potassium carbonate. This reaction can be carried out in various solvents such as tetrahydrofuran, p-dioxane, ethanol and methanol at optimum temperatures ranging from room temperature to 200 ° C. The method of Scheme 1 is illustrated in Step C of Example 1, Steps D1 and D2 of Example 2, and Step B of Example 4.

  As shown in Scheme 2, by reaction with a chlorinating reagent such as phosphorus oxychloride or thionyl chloride, optionally in the presence of a base such as N, N-dimethylaniline, a hydroxy compound of formula 4 (in keto form) The compound of formula 2 can be prepared from (which may be present). The reaction can be carried out as such or in the presence of a solvent such as N, N-dimethylformamide at temperatures ranging from room temperature to 120 ° C. The method of Scheme 2 is illustrated in Step C of Example 1, Steps C1 and C2 of Example 2, and Step B of Example 4.

  As shown in Scheme 3, the compound of formula 4 can be obtained by condensing the amidine of formula 5 and the ketoester of formula 6 in a solvent such as methanol or ethanol at a temperature ranging from room temperature to the reflux temperature of the solvent. Can be manufactured. Optionally, a base such as a metal alkoxide or 1,1,3,3-tetramethylguanidine may be utilized. The method of Scheme 3 is illustrated in Step A of Examples 1 and 4 and Steps A1 and A2 of Example 2.

[Wherein R ⁸⁰ is an alkyl, preferably a carbon moiety such as C ₁ -C ₂ alkyl]

As shown in Scheme 4, halogens such as bromine or N-halosuccinimides in various solvents including acetic acid, N, N-dimethylformamide, dichloromethane and carbon tetrachloride at temperatures ranging from 0-100 ° C. Alternatively, a compound of formula 4 wherein R ³ is halogen can be prepared from a compound of formula 4 where R ³ is hydrogen by reaction with a halogenating reagent such as sulfuryl halide. The method of Scheme 4 is illustrated in Step B of Example 1 and Steps B1 and B2 of Example 2.

Similarly to the method of Scheme 4, a compound of formula I in which R ³ is halogen can also be produced from a compound of formula I in which R ³ is hydrogen by reaction with a halogenating reagent. Such another method is described in Step C of Example 4.

A particularly useful preparation of compounds of formula 4 where R ³ is halogen and R ² is CO ₂ R ¹² is a mixture of dichloromethane, trichloro at temperatures ranging from room temperature to the reflux temperature of the solvent as shown in Scheme 5. A compound of formula 4 wherein R ³ is hydrogen and R ² is CH (OR ¹² ) ₂ in a solvent such as methane or tetrachloromethane, and N-halosuccinimide or bromine (R ³ is bromine) Reaction) with a halogenating reagent and an oxidizing reagent.

Both compounds of formulas 5 and 6 are commercially available or can be prepared by known methods. (Eg, PJ Dunn, Comprehensive Organic Functional Group Transformations, A. R. Katritzky, A. R. Katritzky, A. R. Katritzky) O. Meth-Cohn, edited by C. W. Rees, Pergamon Press; Oxford, 1995; Vol. 5, pages 741-782; T TL Gilchrist, Comprehensive Organic Functional Group Transformations (Comprehensive Organic) Functional Group Transformations, A.R. Katritzky, O. Meth-Cohn, C.W.
. Edited by C. W. Rees, Pergamon Press; Oxford, 1995; Vol. 6, pp. 601-637; R. D. Davis, P.M. J. et al. P.G. Garratt, Comprehensive Organic Synthesis, B.M. M.M. (See B. M. Trost, Pergamon Press; Oxford, 1991; Volume 2, pages 795-803)

Alternatively, as shown in Scheme 6, from a corresponding compound of formula 7 where X ¹ is a leaving group such as a halogen or an alkylsulfonyl group (eg methanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl) Can be manufactured.

[Wherein M ¹ is B (OH) ₂ , Sn (n-Bu) ₃ , MgX ¹ or ZnX ¹ , R ¹ is optionally substituted cyclopropyl, optionally substituted Good isopropyl or optionally substituted phenyl, and X ¹ is a leaving group] This method involves the compound of formula 7 and a boronic acid (eg, M ¹ is B (OH) ₂ ), Organotin reagent (eg, M ¹ is Sn (n-Bu) ₃ ), Grignard reagent (eg, M ¹ is MgX ¹ ) or organozinc reagent (eg, M ¹ is ZnX ¹ ) With a palladium-catalyzed reaction with a compound of formula 8 in the form (E.g., N. Ali, A. McKillop, M. Mitchell, R. Rebelo, A. Ricardo, P. M.). Wall Bank, Tetrahedron, 1992, 48, 8117-8126; J. Solberg, K. Undheim, Acta Chem. Scand. 1989, 43, 62-68, V. Bonnet, (V. Bonnet), F. Mongin, F. Trecourt, G. Queginer and P. Nokel ( P. Knochel) Tetrahedron (Tetrahedron), see 2002,58,4429-4438)

Formulas catalyzed by bases such as triethylamine or potassium carbonate in various solvents including tetrahydrofuran and dichloromethane at temperatures ranging from 0 ° C. to the reflux temperature of the solvent, as shown in Scheme 7. With the amine of 3, the compound of formula 7 in which X ¹ is halogen can be prepared from the dihalo compound of formula 12.

Compounds of formula 12 can be prepared by known methods. (See, for example, H. Gershon, Journal of Organic Chemistry, 1962, 27, 3507-3510)

Also, as shown in Scheme 8, a compound of formula I where R ² is CO ₂ R ¹² can also be prepared from a compound of formula 13 by a carbonylation reaction. Typical conditions are in the presence of a palladium catalyst in a mixture of an alcohol and another solvent such as N, N-dimethylformamide, N-methylpyrrolidinone or tetrahydrofuran at a temperature ranging from room temperature to 150 ° C. And 1 to 10 atmospheres of carbon monoxide.

  As shown in Scheme 9, a compound of formula 13 can be prepared from a compound of formula 14 by reaction with an amine of formula 3 in a reaction similar to the method of Scheme 1.

  As shown in Scheme 10, a compound of formula 14 can be prepared from a diol of formula 15 by reaction with a halogenating reagent such as phosphorus oxychloride or phosphorus oxybromide in a reaction similar to the method of Scheme 2. . (For examples of this method and for the preparation of compounds of formula 15, H. Gershon, R. Braun, A. Scala and R. Rosin (R Rodin), Journal of Medical Chemistry (J. Med. Chem) 1964, 7, 808-811, and MH Norman, N. Chen, Z. Chen ( Z. Chen, C. Fotsch, N. Han, R. Hurt, T. Jenkins, J. Kincaid L. Liu, Y. Lu, O. Moreno, VJ Soundtrack (VJ) Santora), J.D.. Sonenberugu (J.D.Sonnenberg) and W. Carbon (W.Karbon), Journal of Medical Chemistry (J.Med.Chem), see 2000,43,4288-4312)

From a corresponding carboxylic acid compound of formula I (eg R ¹² is H), R ² is an ester functional group (eg CO ₂ R ¹² ) by a wide variety of esterification methods known in the art, R ¹² is other than H) can be prepared. One method is described in Example 3. Conversely, carboxylic acid compounds of formula I can also be prepared from the corresponding ester compounds by a wide variety of hydrolysis methods known in the art, such as saponification.

  It will be appreciated that some of the reagents and reaction conditions described above for preparing compounds of formula I will not be compatible with the particular functional groups present in the intermediate. In these examples, incorporation of protected / deprotected sequences or functional interconversions in the synthesis system will help to obtain the desired product. The use and choice of protecting groups will be apparent to those skilled in the art of chemical synthesis (eg, TW Greene; PGM Wuts) protective GROUPS IN ORGANIC SYNTHESIS, 2nd edition; see Wiley: New York, 1991). In some cases, after introduction of a given reagent as described in any individual scheme, additional conventional synthetic steps not described in detail are performed to complete the synthesis of the compound of formula I Those skilled in the art will recognize that this is necessary. One skilled in the art will also recognize that the combinations of steps illustrated in the above scheme need to be performed in an order other than that shown by the particular order proposed for preparing compounds of Formula I.

  To add substituents or modify existing substituents, the compounds of formula I and intermediates described herein can be subjected to various electrophilic, nucleophilic, group, organometallic, oxidation and reduction reactions. Those skilled in the art will also recognize that they can be accepted.

Without further details, it is believed that one skilled in the art using the foregoing can utilize the present invention to its fullest extent. Accordingly, the following examples are to be construed as merely illustrative and are not intended to limit the present disclosure to any form. The steps in the following examples describe the procedure for each step in the total synthetic conversion, and the starting materials for each step are not necessarily manufactured by the specific manufacturing practice described in the other examples or steps. May be. Percentages are by weight except for chromatographic solvent mixtures or unless otherwise specified. Unless otherwise noted, parts and percentages with respect to chromatographic solvent mixtures are by volume. ¹ H NMR spectra are reported at ppm low magnetic fields from tetramethylsilane. “S” means singlet, “d” means doublet, “t” means triplet, “q” means quartet, “m” means multiplet "Dd" means doublet doublet, "ddd" means doublet doublet doublet, "dt" means triplet doublet, “Dq” means a quartet doublet, “br s” means a broad singlet, and “br d” means a broad doublet.

Example 1
Process for producing ethyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate (Compound 1) and methyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate (Compound 2) A: Preparation of 2-cyclopropyl-6- (diethoxymethyl) -4 (1H) -pyrimidinone Ethyl 4,4-diethoxy-3-oxobutanoate (E. Graf), R in methanol (100 mL) Prepared according to the method of R. Troschutz, Synthesis, 1999, 7, 1216; 10.0 g, 46 mmol) and cyclopropanecarboximidamide monohydrochloride (Lancaster Synthesis), 5.0 g, 41 mm ) In a mixture of, sodium methoxide in methanol (5.4 M, 8.4 mL, 46 mmol) was added. The reaction mixture was stirred overnight. The solvent was removed by a rotary evaporator. Dichloromethane was added and the mixture was filtered. The solvent was removed from the filtrate by rotary evaporator. The residue was purified by medium pressure liquid chromatography (MPLC) (35 → 100% ethyl acetate in hexane as eluent) to give the title compound as a white solid (4.67 g).

¹ H NMR (CDCl ₃ ) δ 6.55 (s, 1H), 5.10 (s, 1H), 3.61 (m, 4H), 1.91 (m, 1H), 1.23 (m, 8H) ), 1.09 (m, 2H)

  In addition, 3.24 g of non-dehydrated product was obtained. This material could be converted to the title compound by refluxing in methanol with a catalytic amount of pyridinium p-toluenesulfonate.

Step B: Preparation of ethyl 5-bromo-2-cyclopropyl-1,6-dihydro-6-oxo-4-pyrimidinecarboxylate 2-cyclopropyl-6- (diethoxymethyl) -4 (in dichloromethane (75 mL) To a solution of 1H) -pyrimidinone (ie, the title product of Step A) (2.9 g, 12.1 mmol) was added N-bromosuccinimide (4.76 g, 26.8 mmol). The reaction mixture was stirred overnight. The solvent was removed by a rotary evaporator. The residue was purified by MPLC (1 → 4% methanol in dichloromethane as eluent) to give the title compound as a white solid (2.68 g).

¹ H NMR (CDCl ₃ ) δ 4.43 (q, 2H), 1.90 (m, 1H), 1.41 (t, 3H), 1.30 (m, 2H), 1.20 (m, 2H) )

Step C: Preparation of ethyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate and methyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate N, N-dimethylformamide (15 mL) solution of ethyl 5-bromo-2-cyclopropyl-1,6-dihydro-6-oxo-4-pyrimidinecarboxylate (ie, the product of Step B) (1.07 g, 3.7 mmol) Was added thionyl chloride (0.54 mL, 7.5 mmol). The reaction mixture was stirred for 2 hours. The solvent was removed by a rotary evaporator. The residue was dissolved in dichloromethane and washed with saturated aqueous sodium bicarbonate and dried (Na ₂ SO ₄ ). The solvent was removed by a rotary evaporator. The residue was dissolved in tetrahydrofuran (2 mL) and ammonia in methanol (7N, 2 mL) was added. The reaction mixture was placed in a sealed Bayer bottle and heated in a microwave reactor at 125 ° C. for 2 hours. The reaction mixture was allowed to stand for 1 week. Dichloromethane was added and the reaction mixture was filtered. The solvent was removed by a rotary evaporator. The residue was purified by MPLC (10 → 30% ethyl acetate in hexane as eluent) to give the title product, a compound of the invention, as a white solid (0.52 g).

¹ H NMR (CDCl ₃ ) δ 5.40 (br s, 2H), 4.44 (q, 2H), 2.05 (m, 1H), 1.01 (t, 3H), 1.05 (m, 2H), 0.99 (m, 2H)

  The corresponding methyl ester which is a further compound of the invention, ie methyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate, was also isolated from MPLC purification as a white solid (0.06 g).

¹ H NMR (CDCl ₃ ) δ 5.40 (br s, 2H), 3.97 (s, 3H) 2.05 (m, 1H), 1.05 (m, 2H), 0.99 (m, 2H) )

Example 2
Step A1: Production of 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid (Compound 135) Production of 2-cyclopropyl-1,6-dihydro-6-oxo-4-pyrimidinecarboxylic acid 30 To a mixture of diethyl oxalate acetate sodium salt (150 g, 714 mmol) in methanol (300 mL) and water (150 mL) warmed to 0 ° C., 50% aqueous sodium hydroxide solution (56 g, 700 mmol) in water (60 mL) Was added over 30 minutes while maintaining the temperature at 25-30 ° C. and the pH at 11-12. The stirred mixture was then heated at 35 ° C. for an additional 30 minutes. To this mixture was added cyclopropane carboxyimidamide monohydrochloride (64 g, 530 mol) in one portion over 15 minutes. The orange solution was heated to 50 ° C. over 30 minutes and held at this temperature for 3 hours. The reaction mixture was cooled to 35 ° C. and concentrated hydrochloric acid (about 70 g, 0.7 mol) was added slowly (foaming) at 30-40 ° C. over 30 minutes until the pH was about 1.5-2.5. was gotten). The mixture was concentrated on a rotary evaporator at 35-40 ° C. to remove the alcohol and stirred at 25 ° C. for 3-4 hours to complete crystallization of the product. After the mixture was cooled to 0 ° C., the solid was collected by filtration. The solid was washed with water (2 × 60 mL), sucked dry, then dried in a vacuum oven at 60 ° C. to give the title compound as a beige solid (ca. 60 g).

¹ H NMR (DMSO-d ₆ ) δ 6.58 (s, 1H), 1.95 (m, 1H), 1.0 (m, 4H)

Step A2: Another Preparation of 2-Cyclopropyl-1,6-dihydro-6-oxo-4-pyrimidinecarboxylic acid Diethyloxal acetate sodium salt (210 g, 950 mmol) in methanol (500 mL) and water (400 mL) ) Was added over 30 minutes with 50% aqueous sodium hydroxide in water (60 mL), during which time the temperature was maintained at 25-30 ° C. and the pH at 11-12. The stirred mixture was then heated at 30 ° C. for an additional 30 minutes. To this mixture was added cyclopropane carboxyimidamide monohydrochloride (110 g, 910 mol). The orange solution was heated to 50 ° C. over 30 minutes and held at this temperature for 5 hours. The reaction mixture is cooled to 30 ° C., concentrated to half volume under reduced pressure at 35-40 ° C., and concentrated hydrochloric acid (140 g, until pH is about 1-2 at 25-30 ° C. over 30 minutes. 1.4 mol) was added slowly (foaming was obtained). The mixture was stirred at 5 ° C. for 1 hour to complete crystallization of the product. After the mixture was cooled to 0 ° C., the solid was collected by filtration. The solid was washed with water (3 × 60 mL), sucked dry, then dried in a vacuum oven at 70 ° C. to give the title compound as a beige solid (100 g); m. p. 235-236 ° C. (dec.).

¹ H NMR (DMSO-d ₆ ) δ 6.58 (s, 1H), 1.95 (m, 1H), 1.0 (m, 4H)

Step B1: Preparation of 5-chloro-2-cyclopropyl-1,6-dihydro-6-oxo-4-pyrimidinecarboxylic acid 2-cyclopropyl-1,6-dihydro-6 in water (30 mL) at 15 ° C. In a mixture of oxo-4-pyrimidinecarboxylic acid (ie, the product of step A1 or A2) (9.2 g, 52 mmol) and concentrated hydrochloric acid (22 g, 220 mmol), the reaction mixture is maintained at 15-20 ° C. With cooling, a sodium hypochlorite aqueous solution (11%, 40 g, 59 mmol) was added dropwise over 15 minutes. The mixture was then held at 20-25 ° C. for 1 hour. Solid sodium bisulfite (about 2 g) is added, followed by dropwise addition of aqueous sodium hydroxide (50%, 8 g, 0.10 mol) while cooling the reaction mixture to maintain at about 25 ° C. did. The mixture was cooled to 10 ° C., the suspended product was isolated by filtration and washed with a minimum amount of cold water. The product was then dried in a vacuum oven at 50 ° C. until constant weight to give the title compound (7.5 g).

¹ H NMR (DMSO-d ₆ ) δ 13.4 (br s, 1H), 1.95 (m, 1H), 1.0 (m, 4H)

Step B2: Another Preparation of 5-Chloro-2-cyclopropyl-1,6-dihydro-6-oxo-4-pyrimidinecarboxylic acid 2-Cyclopropyl-1,6 in water (45 mL) at 8-12 ° C A mixture of dihydro-6-oxo-4-pyrimidinecarboxylic acid (ie the product of step A1 or A2) (184 g, 1.02 mol) and concentrated hydrochloric acid (292 g, 3 mol) was added to Aqueous sodium hypochlorite solution (8.4%, 1.02 kg, 1.15 mol) was added dropwise over 2 hours while cooling to maintain the temperature. The mixture was then held for 1 hour at 10-12 ° C. and conversion was monitored by HPLC. When the remaining amount of starting material was less than 5%, solid sodium bisulfite was added until a negative KI starch paper test was obtained. The mixture was cooled to 5 ° C., the suspended product was isolated by filtration and washed with a minimum amount of cold water. The product was then dried to constant weight at 50 ° C. in a vacuum oven to give the title compound (194 g); m. p. 189-190 ° C.

¹ H NMR (DMSO-d ₆ ) δ 13.4 (br s, 1H), 1.95 (m, 1H), 1.0 (m, 4H)

Step C1: Preparation of 5,6-dichloro-2-cyclopropyl-4-pyrimidinecarboxylic acid Phosphorus oxychloride (14 mL, 23 g, 0.15 mol) and 5-chloro-2-cyclopropyl-1,6-dihydro- 6-Oxo-4-pyrimidinecarboxylic acid (ie, the product of Step B1 or B2) (75 g, 300 mmol) was combined and heated at 85 ° C. for 3 hours. The reaction mixture is cooled to 30 ° C. and the temperature is maintained at 5-10 ° C. and acetonitrile is maintained over 30 minutes while maintaining the pH in the range of 1-3 by co-feeding aqueous ammonia (28%). (50 mL) and ice water (80 mL) were added to the mixture. The pH was adjusted to about 2, the mixture was concentrated on a rotary evaporator at 25 ° C. to remove acetonitrile, and the precipitated product was isolated by filtration and washed with water (2 × 25 mL). The solid was dried in a vacuum oven to give the title compound (about 7.0 g).

¹ H NMR (DMSO-d ₆ ) δ 2.23 (m, 1H), 1.2 (m, 2H), 1.0 (m, 2H)

Step C2: Another Preparation of 5,6-Dichloro-2-cyclopropyl-4-pyrimidinecarboxylic acid Phosphorus oxychloride (200 mL, 328 g, 2.14 mol) and 5-chloro-2-cyclopropyl-1,6 -Dihydro-6-oxo-4-pyrimidinecarboxylic acid (ie the product of step B1 or B2) (96.8 g, 451 mmol) was combined and heated at 90 ° C for 5 hours. The reaction mixture was cooled to 50-60 ° C. and concentrated under reduced pressure to half volume. After cooling to 30 ° C., the reaction mixture was added to a mixture of t-butanol (200 mL) and water (300 mL) over 60 minutes while maintaining the temperature at 8-10 ° C. The mixture was seeded, water (300 mL) was added slowly at 10-15 ° C. and the mixture was stirred for 1 hour. After cooling to 5 ° C., the precipitated product was isolated by filtration and washed with water (3 × 50 mL). The solid was dried in a vacuum oven to give the title compound (93 g).

¹ H NMR (DMSO-d ₆ ) δ 2.23 (m, 1H), 1.2 (m, 2H), 1.0 (m, 2H)

Step D1: Preparation of 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid 5,6-Dichloro-2-cyclopropyl-4-pyrimidinecarboxylic acid (ie, product of Step C1 or C2) A mixture of (5.1 g, 22 mmol), water (30 mL) and aqueous ammonia (28%, 8 g, 130 mmol) was heated at 80 ° C. for 3 hours. The solution was concentrated at 50 ° C. and 70 torr (9.3 kPa) pressure to about half volume to remove most of the excess ammonia. The resulting slurry was stirred at 20 ° C., acidified to pH 2 with aqueous hydrochloric acid, cooled to 5 ° C. and filtered. The isolated solid was dried in a vacuum oven to give the title product (4.2 g), a compound of the invention.

¹ H NMR (DMSO-d ₆ ) δ 13.4 (br s, 1H), 1.95 (m, 1H), 1.0 (m, 4H)

Step D2: Another Preparation of 6-Amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid 5,6-Dichloro-2-cyclopropyl-4-pyrimidinecarboxylic acid (ie, of step C1 or C2 A mixture of (product) (280 g, 1.2 mol), water (1.26 L) and aqueous ammonia (28%, 350 g, 5.76 mol) was heated at 80 ° C. for 5 hours. The solution was concentrated at 50 ° C. and 70 torr (9.3 kPa) pressure to about half volume to remove most of the excess ammonia. The resulting slurry was stirred at 20 ° C., acidified to pH 1-2 with aqueous hydrochloric acid, cooled to 5 ° C. and filtered. The isolated solid was dried in a vacuum oven to give the title product (270 g), a compound of the invention.

¹ H NMR (DMSO-d ₆ ) δ 13.4 (br s, 1H), 1.95 (m, 1H), 1.0 (m, 4H)

Example 3
Preparation of methyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate (Compound 9) 6-Amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid in methanol (20 mL) (ie To a solution of Example 2, Step D1 or D2 product) (2.0 g, 8.5 mmol), thionyl chloride (4 mL, 70 mmol) was added dropwise. The mixture was heated under reflux for 24 hours. Concentrated sulfuric acid (5 drops) was added and the reaction mixture was heated at reflux for 16 hours. After cooling the mixture, water (30 mL) was added and aqueous ammonia (28%, 10 mL) was added dropwise. The mixture was cooled to 5 ° C. and the solid was isolated by filtration, washed with water and dried in a vacuum oven at 40 ° C. to give the title product (2.3 g), a compound of the invention.

¹ H NMR (CDCl ₃ ) δ 5.41 (br s, 2H), 3.98 (s, 3H), 2.06 (m, 1H), 1.04 (m, 2H), 1.00 (m, 2H)

Another Preparation of Methyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate 6-Amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid in methanol (120 mL) with cooling To a solution of the acid (ie the product of step D1 or D2 of Example 2) (8.5 g, 40 mmol) thionyl chloride (15 mL, 200 mmol) was added dropwise. The mixture was heated at 60 ° C. for 24 hours. The mixture was concentrated to 25% of the initial volume and diluted with water (100 mL). Phenolphthalein pH indicator was added, and while cooling to 10-20 ° C, 10% aqueous sodium hydroxide was added dropwise to bring the pH to 8-10. The solid was isolated by filtration, washed with water and dried in a vacuum oven at 50-60 ° C. to give the title product (7.3 g), a compound of the invention.

¹ H NMR (CDCl ₃ ) δ 5.41 (br s, 2H), 3.98 (s, 3H), 2.06 (m, 1H), 1.04 (m, 2H), 1.00 (m, 2H)

Example 4
Production process A of 6-amino-5-chloro-2- (4-chlorophenyl) -4-pyrimidinecarboxylic acid (compound 65): 2- (4-chlorophenyl) -1,6-dihydro-6-oxo-4- Preparation of pyrimidinecarboxylic acid To a mixture of diethyl oxalacetate sodium salt (123.2 g, 586 mmol) in water (750 mL) was added aqueous sodium hydroxide (50%, 47 g, 586 mmol) slowly. After 1 hour, the solid dissolved. 4-Chlorobenzenecarboximidamide monohydrochloride (111.95 g, 586 mmol) was then added and the mixture was heated at 70 ° C. overnight. After cooling to room temperature, concentrated hydrochloric acid was slowly added (foaming occurred) until the pH dropped to 1.5. The solid was isolated by filtration and washed with water and methanol. The solid was then triturated twice with hot methanol, washed repeatedly with 1N hydrochloric acid, then once with methanol and dried to give the title compound (66.07 g).

¹ H NMR (DMSO-d ₆ ) δ 8.23 (d, 2H), 7.65 (d, 2H), 6.90 (s, 1H)

Step B: Preparation of 6-amino-2- (4-chlorophenyl) -4-pyrimidinecarboxylic acid 2- (4-chlorophenyl) -1,6-dihydro-6-oxo-4-pyrimidine was added to phosphorus oxychloride (180 mL). Carboxylic acid (ie the product of Step A) (81.81 g, 326 mmol) was added. The mixture was heated to 90 ° C. for 2.5 hours. After cooling to room temperature, the reaction mixture was slowly added to 1: 2 acetonitrile: water (1.5 L) while maintaining the temperature between 35 ° C. and 45 ° C. After the reaction mixture was stirred for 30 minutes at room temperature, the resulting solid was isolated by filtration and washed with water. The solid was then combined with aqueous ammonia (5%, 2.1 L) and heated to 80 ° C. for 18 hours. After 2 days at room temperature, the solid was isolated by filtration and washed with water. A second yield was obtained by cooling and refiltering the filtrate. The combined solids were dried to give the title compound (58.8 g).

¹ H NMR (DMSO-d ₆ ) δ 8.33 (d, 2H), 7.51 (d, 2H), 6.89 (s, 2H), 6.81 (s, 1H)

Step C: Preparation of 6-amino-5-chloro-2- (4-chlorophenyl) -4-pyrimidinecarboxylic acid 6-amino-2- (4-chlorophenyl) in N, N-dimethylformamide (300 mL) at 50 ° C To a solution of -4-pyrimidinecarboxylic acid (ie, the product of Step B) (75 g, 300 mmol) was added N-chlorosuccinimide (44.1 g, 330 mmol) in one portion. An exotherm increased the temperature of the reaction mixture to 65 ° C. The reaction mixture was then heated at 55 ° C. for 3 hours. Additional N-chlorosuccinimide (14 g, 90 mmol) was added in one portion and the reaction mixture was maintained at 55 ° C. for 30 minutes. After cooling the reaction mixture, water was added. The resulting solid was isolated by filtration, washed with water, dissolved in ethyl acetate, washed with water and dried. The solvent was removed using a rotary evaporator to give the title product, a compound of the invention, as a tan solid (73.68 g).

¹ H NMR (DMSO-d ₆ ) δ 8.28 (d, 2H), 7.70 (br s, 2H), 7.58 (d, 2H)

Example 5
Preparation of ethyl 6-amino-5-chloro-2- (4-chlorophenyl) -4-pyrimidinecarboxylate (Compound 64) 6 in ethanol (70 mL) while maintaining a temperature below 15 ° C. using an ice bath. A solution of amino-5-chloro-2- (4-chlorophenyl) -4-pyrimidinecarboxylic acid (ie the product of Example 4, Step C) (20.0 g, 70.4 mmol) in thionyl chloride (5 .14 mL, 70.4 mmol) was added. The reaction mixture was then heated at reflux overnight. Water was added. Next, with external cooling, an aqueous sodium hydroxide solution (50%) was added to adjust the pH to 7. The resulting solid was isolated by filtration and dried to give the title product, a compound of the invention, as a light beige solid (20.1 g).

¹ H NMR (CDCl ₃ ) δ 8.31 (d, 2H), 7.42 (d, 2H), 5.50 (brs, 2H), 4.50 (q, 2H), 1.47 (t, 3H)

The compounds in Tables 1-4 below can be made by procedures described herein, along with methods known in the art. In the tables, the following abbreviations are used: t means tertiary, i means iso, Me means methyl, Et means ethyl, Pr means propyl, i- Pr means isopropyl, Bu means butyl, t-Bu means tert-butyl, CN means cyano, and S (O) ₂ Me means methylsulfonyl. “ ⁻ ” Means a negative formal charge and “ ⁺ ” means a positive formal charge.

Formulation / Efficacy The compounds of the present invention are generally used as a formulation or composition with an agriculturally suitable carrier comprising at least one liquid diluent, solid diluent or surfactant. The formulation or composition component is selected to match the physical properties of the active ingredient, the mode of application, and environmental factors such as soil type, humidity and temperature. Useful formulations may optionally be concentrated into gels, such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and / or suspoemulsions), etc. Contains a lot of liquid. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films (including seed coatings) and the like that may be water dispersible ("hydrated") or water soluble. The active ingredient can be (micro) encapsulated and further formed into a suspension or solid formulation, or the entire formulation of active ingredient can be encapsulated (or “overcoated”). Encapsulation can control or delay the release of the active ingredient. The sprayable formulation can be applied to a suitable medium and can be used at a spray volume of about 1 to several hundred liters per hectare. The high strength composition is first used as an intermediate for further formulation.

  Formulations typically contain effective amounts of active ingredients, diluents and surfactants within the appropriate range of addition to the following 100% by weight.

  Exemplary solid diluents include those of Watkins et al., Handbook of Insectide Dusted Diluents and Carriers, 2nd edition, Dorland Books, Caldwell. ), New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide 2nd Edition, Interscience, New York, 1950. McCutcheon's Detergents and Emulsifiers Annual, Allred Publishing Corp. (W) and New Jersey (W), Ridgewood (R) and Ridgewood (R) , Encyclopedia of Surface Active Agents, Chemical Publishing Company, Inc., New York, 196, Encyclopedia of Surface Active Agents, Chemical Publishing Company, Inc., New York, 196 It describes the use of surfactants and recommended. All formulations can contain small amounts of additives to reduce foaming, caking, corrosion, microbial growth, etc., or thickeners to increase viscosity.

Examples of the surfactant include polyethoxylated alcohol, polyethoxylated alkylphenol, polyethoxylated sorbitan fatty acid ester, dialkylsulfosuccinate, alkylsulfate, alkylbenzenesulfonate, organosilicone, N, N-dialkyltaurate, lignin. The number of glucose units called sulfonate, naphthalenesulfonate formaldehyde condensate, polycarboxylate, glycerol ester, polyoxyethylene / polyoxypropylene block copolymer, and degree of polymerization (DP) can range from 1 to 3 and alkyl polyglycosides alkyl units can range from _C 6 _{-C 14} (Pure and Applied chemistry (Pure and Applied Chemist y) 72,1255-1264 see) and the like. Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and sodium bicarbonate, and sodium sulfate. Examples of the liquid diluent include water, N, N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, propylene carbonate, dibasic ester, paraffin, alkylbenzene, alkylnaphthalene, glycerin and triacetin. , Olive oil, castor oil, linseed oil, tung oil, sesame oil, corn oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil and coconut oil, fatty acid ester, cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone Ketones such as hexyl acetate, acetate esters such as heptyl acetate and octyl acetate, and methanol, cyclohexanol, decanol, benzyl and tetrahydrofurfuryl al They include alcohols such as Lumpur.

  Useful formulations of the present invention may contain materials well known to those skilled in the art as formulation aids such as antifoams, film forming elements and dyes. Antifoaming agents include water dispersible liquids comprising a polyorganosiloxane such as Rhodorsil® 416. Film forming elements include polyvinyl acetate, polyvinyl acetate copolymer, polyvinyl pyrrolidone-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl alcohol copolymer and wax. Examples of the dye include water-dispersible liquid pigment compositions such as Pro-lzed (registered trademark) Carlant Red. Those skilled in the art will recognize that this is not a complete list of formulation adjuvants. Suitable examples of formulation aids include those described herein, as well as McCutcheon's 2001, published by MC Publishing Company, Volume 2: Functional Materials ( Functional materials) and those described in International Publication No. 03/024222 pamphlet.

  By simply mixing the components, a solution containing the emulsifiable concentrate can be produced. Dusts and powders can be produced by blending and usually grinding in a hammer mill or fluid energy mill. The suspension is usually produced by wet grinding. See, for example, US Pat. No. 3,060,084. Granules and pellets can be produced by spraying the active material onto preformed granule carriers or by agglomeration techniques. Browning, “Agglomeration”, Chemical Engineering, December 4, 1967, pp. 147-48, Perry's Chemical Engineer's Handbook, See 4th edition, McGraw-Hill, New York, 1963, pp. 8-57 and below and WO 91/13546. Pellets can be produced as described in US Pat. No. 4,172,714. Water dispersible and water soluble granules can be prepared as taught in US Pat. No. 4,144,050, US Pat. No. 3,920,442 and DE 3,246,493. Tablets can be manufactured as taught in US Pat. No. 5,180,587, US Pat. No. 5,232,701 and US Pat. No. 5,208,030. Films can be made as taught in GB 2,095,558 and US Pat. No. 3,299,566.

For more information on the field of formulation, see T.W. S. “The Formulas Toolbox for Product Forms in the Woods, Pesticide Chemistry and Bioscience, The Food-Environment Challenge” (The Formulator's Toolbox-Product Forms for Modern Aggregate), "T. Brooks and T. Brooks R. Edited by Roberts, Proceedings of the 9th International Congress on Pesticide Chemistry, and the Royal Society of Chemistry 1999, 120-133. U.S. Pat. No. 3,235,361, column 6, lines 16-7, line 19 and Examples 10-41; U.S. Pat. No. 3,309,192, column 5. Lines 43-7, Line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167, and 169-182; US Patents No. 2,891,855, column 3, lines 66-5, line 17, and Examples 1-4; Klingman, Weed Control as a Science, John Willie and Sons, Inc. (John Wiley
and Sons, Inc., New York, 1961, pp. 81-96; Hance et al., Weed Control Handbook (Weed)
Control Handbook), 8th edition, Blackwell Scientific Publications, Oxford, 1989; and Developments in FormationJ, B
See also Publications, UK, Richmond, UK, 2000.

  In the following examples, all percentages are by weight and all formulations are made by conventional methods. Compound numbers refer to compounds in Index Tables AD.

The test results indicate that the compounds of the invention are very active pre-emergence and / or post-emergence herbicides and / or plant growth regulators. Areas where complete control of all vegetation is desired, such as around fuel storage tanks, industrial storage, parking lots, drive-in theaters, airfields, riverbanks, irrigation and other waterways, billboards and around main roads and railway structures Many of them have utility regarding pre-emergence and / or post-emergence weed control, which are widely used in Many of the compounds of the present invention are selective by selective metabolism of crops versus weeds, by selective activity of physiological repression positions in crops and weeds, or in the environment or environment of a mixture of crops and weeds. The arrangement is useful for selective suppression of grass and broadleaf weeds within crop / weed mixtures. One skilled in the art will recognize that a preferred combination of these selectivity factors within a compound or group of compounds can be readily determined by performing routine biological and / or biochemical assays. . The compounds of the present invention include, but are not limited to, alfalfa, barley, cotton, wheat, rape, sugar beet, corn (corn), sorghum, soy, rice, oats, peanuts, vegetables, tomatoes, potatoes, perennial plantation crops such as Tea and forests such as coffee, cocoa, oil palm, rubber, sugar cane, citrus, grapes, fruit trees, nut trees, bananas, plantains, pineapples, hops, eucalyptus and conifers (e.g. loblolly pine), and turf species ( For example, Kentucky bluegrass, St. Augustine glass, Kentucky fescue, and Bermuda gra It may exhibit resistance to important crops including s)). Genetically incorporated to incorporate herbicide tolerance, express a protein that is toxic to invertebrate pests (eg, Bacillus thuringiensis toxin), and / or express other useful traits The compounds of the invention can be used in converted or breeded crops. One skilled in the art will recognize that not all compounds are equally effective against all weeds. Alternatively, the subject compounds are useful for altering plant growth.

  Since the compounds of the present invention have both pre-emergence and post-emergence herbicidal activity, an herbicidally effective amount to suppress undesirable vegetation by killing or damaging the vegetation or reducing its growth Of the present invention or a composition comprising said compound and at least one of a surfactant, solid diluent or liquid diluent on the leaves or other parts of unwanted vegetation, or unwanted vegetation grows Alternatively, the compounds can be effectively applied by a variety of methods involving contact with undesired vegetation environments such as soil or water surrounding undesired vegetation seeds or other pearls.

  The herbicidally effective amount of the compounds of the invention is determined by a number of factors. These factors include the formulation selected, the method of application, the amount and type of vegetation present, the growth conditions, and the like. In general, herbicidally effective amounts of the compounds of the present invention are from about 0.0001 kg / ha to 20 kg / ha, with a preferred range of about 0.001 kg / ha to 5 kg / ha, and a more preferred range. Is about 0.004 kg / ha to 3 kg / ha. One skilled in the art can readily determine the herbicidally effective amount required for the desired level of weed control.

The compounds of the present invention can be used alone or in combination with other herbicides, insecticides and fungicides, and other agricultural chemicals such as fertilizers. Mixtures of the compounds of the present invention with other herbicides can expand the range of activity against additional weed species and can suppress the growth of any resistant biotype. Mixtures of one or more of the following herbicides with the compounds of the present invention may be particularly useful for weed control: acetochlor, acifluorfen and its sodium salt, aclonifen, acrolein (2-propenal) , Alachlor, alloxydim, ametrine, amicarbazone, amidosulfuron, aminopyralide, amitrolol, ammonium sulfamate, anilofos, zulfurulm beflubutamid), benazoline, benazoline-ethyl, ben Rurarin, benfuresate (benfuresate), bensulfuron (bensulfuron) - methyl, bensulide, bentazone (bentazone), benzobicyclon (benz
obicyclon, benzofenap, bifenofox, bilanafos, bispyribac and its sodium salt, bromacil, bromobutide, bromophenoxym, bromoxynyl, butanocylbutanoyl Butralin, butroxydim, butyrate, caffentrol, carbetamide, carfentrazone-ethyl, catechin, chloromethoxyphene, chloramphene, chloramben Romulone, chlorflumenol-methyl, chloridazone, chlorimuron-ethyl, chlorotolulone, chlorprofam, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, cinidon-ethyl, cinmethyl , Cinosulfuron, cleoxydim, clethodim, clodinafop-propargyl, clomazone, cloproliprim, cloproprolim nsulam) -methyl, copper sulfate, CUH-35 (2-methoxyethyl 2-[[[4-chloro-2-fluoro-5-[(1-methyl-2-propynyl) oxy] phenyl] (3-fluorobenzoyl) ) Amino] carbonyl] -1-cyclohexene-1-carboxylate), cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop-butyl, 2,4- D and its butyl, butyl, isooctyl and isopropyl esters and their dimethylammonium, diolamine and trolamine salts, diemron, dalapon, dalapon-sodium, dazomet, 2,4-DB and its dimethyl Tillammonium, potassium and sodium salts, desmedifam, desmethrin, dicamba, and its diglycolammonium, dimethylammonium, potassium and sodium salts, diclobenil, dichloroprop, diclofop-methyl, diclosram, methyl Diphenzoquat sulfate, diflufenican, diflufenzopyr, dimeflon, dimethylpiperate, dimethachlor, dimetamethrin, dimethylene, dimethenamide, dimethenamide in dimethenamide Rucinic acid and its sodium salt, dinitramine, dinoterb, diphenamide, diquat dibromide, dithiopyr, diuron, DNOC, endothal, epoprodan, EPTC, esprocarb, etalfluralin et, ethamuluron -Methyl, etofumesate, ethoxyphene, ethoxysulfuron, etozanzanid, phenoxaprop-ethyl, phenoxaprop-P-ethyl, fentrazuron f TCA Flampprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulfam, fluazihop-butyl, fluazihop-P-butyl, flukacarbazone, sodium flukazone Flucetosulfuron, fluchloraline, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumilorac-pentyl, flumioxazine, flumioxazine, flumioxazine
oglycofen) -ethyl, flupirsulfuron-methyl and its sodium salt, flulenol, flulenol-butyl, fluridone, flurochloridone, fluroxypyr, flulutamethole Fomesafen, foramsulfuron, fosamine-ammonium, glufosinate, glufosinate-ammonium, glyphosate and its salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimedium ( t imesium (alternatively called sulfosate), halosulfuron-methyl, haloxyhop-ethyl, haloxyhop-methyl, hexazinone, HOK-201 (N- (2,4-difluorophenyl) -1,5-dihydro-N -(1-methylethyl) -5-oxo-1-[(tetrahydro-2H-pyran-2-yl) methyl] -4H-1,2,4-triazole-4-carboxamide), imazametabenzen-methyl , Imazamox, imazapic, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazetapylammonium Zosulfuron, indanophan, iodosulfuron-methyl, oxynulyl, oxonyl octanoate, oxonyl-sodium, isoproturon, isouron, isoxaflule, isoxaflule, isoxaflule Xoxachlortole, isoxadifen, KUH-021 (N- [2-[(4,6-dimethoxy-2-pyrimidinyl) hydroxymethyl] -6- (methoxymethyl) phenyl] -1,1- Difluoromethanesulfonamide), lactofen, renacil, linuron, maleic acid Dorazide, MCPA and its salts (eg MCPA-dimethylammonium, MCPA-potassium and MCPA-sodium), esters (eg MCPA-2-ethylhexyl, MCPA-butyl) and thioesters (eg MCPA-thioethyl), MCPB and its Salts (eg, MCPB-sodium) and esters (eg, MCPB-ethyl), mecoprop, mecoprop-P, mefenacet, mefluidide, mesosulfuron-methyl, mesotrione, metam-sodium, metamihope ), Metamitron, metazachlor, metabenzthiazulone, methylarson And its calcium, monoammonium, monosodium and disodium salts, methyl dimuron, metbenzuron, metobromurone, metolachlor, S-metholachlor, metosuram, metoxuron, metriburon, metsulfuron, metsulfuron, metsulfuron Methyl, molinate, monolinuron, naproanilide, napropamide, naptalam, nebulon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiaargyl, oxadiazon, oxasulfuron (oxasulfuron) ziclomephone), oxyfluorfen, paraquat dichloride, pebrate, pelargonic acid, pendimethalin, penoxsulam, pentanochlor, pentoxoneone, diflumone, thorium, diflumone , Picolinafen, pinoxaden, piperofos, pretilachlor, primisulfuron-methyl, prodiamine, diphloprodim Lometon, promethrin, propachlor, propanil, propaquiazohop, propazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propyzamide (pro) urro sul Pyraclonil, pyraflufen-ethyl, pyrazogyl, pyrazolate, pyrazolynate, pyrazoxyfen, pyrazosulfuron, pyrazosulfuron (Pyribenzoxim), piributicarb, pyridate, pyriftalid, pyriminobac-methyl, pyrithiobac, cine Quizalofop-ethyl, Quizalofop-P-ethyl, Quizalofop-P-tefuryl, rimsulfuron, cetoxydim, sidulone, simazine, simetrin, sulcotrione, ulfentrazone (e) Sulfometuron-methyl, sulfosulfuron, 2,3,6-TBA, TCA, TCA-sodium, tebutam, tebuthiuron, tepraxidim, terbacil, terbumeton, terbuthetine (Terbuthylazine), terbutryn, tenylchlor, thiazopyr, thifensulfuron-methyl, thiobencarb, thiocarbyl (thiocarbyl) riasulfuron, triaziflam, tribenuron-methyl, triclopyr, triclopyr-butyl, triclopyr-triethylammonium, tridiphane, trietazine, triflifuron, triflifuron Methyl, tritosulfuron and vernolate. Other herbicides include Alternaria destoluen simmons, Coretotrisham gloeospoliodos (pens) Pens. & Sack. (Colletotrichum gloeosporides (Penz.) Penz. & Sacc.), Drechiera monoceras (MTB-951), Mirothecium bercania (Albertini & Schwein) ditmer: Phytofutra Palmybora (Butor.) Butor. Also included are biological herbicides such as (Phytophthora palmivora (Butl.) Butl.) And Puccinia thlaspeos Schub. Combinations of the compounds of the present invention with other herbicides provide a higher (ie, synergistic) effect on the weeds and / or a lower (ie, safer) effect than the additive effect on crops or Obtained on other desired plants. In certain instances, combinations with other herbicides with similar ranges of inhibition but different modes of action are particularly advantageous to prevent the development of resistant weeds. Herbicidally effective amounts of the compounds of the present invention as well as herbicidally effective amounts of other herbicides can be readily determined by one of ordinary skill in the art through simple experimentation.

Diuron, hexazinone, terbacil, bromacil for good control of undesirable vegetation (eg, lower utilization, broader weed control, or crop safety enhancement) or to prevent the development of resistant weeds Glyphosate (especially glyphosate-isopropylammonium, glyphosate-sodium, glyphosate-potassium, glyphosate-trimedium), glufosinate (especially glufosinate-ammonium), azimusulfuron, chlorsulfuron, etamethsulfuron-methyl, Chlorimuron-ethyl, bensulfuron-methyl, rimsulfuron, sulfometuron-methyl, metsulfuron-methyl, nicosulfuron, tribenuron-methyl, thifensulfuron-methyl, flupirsulfuron- Chill, flupylsulfuron-methyl-sodium, halosulfuron-methyl, primsulfuron-methyl, trifloxysulfuron, foramsulfuron, mesosulfuron-methyl, iodosulfuron-methyl, isoproturon, amethrin, amitrol, paraquat Dichloride, diquat dibromide, atrazine, metribudine, acetochlor, metolachlor, S-metolachlor, alachlor, pretilachlor, cetoxydim, tolalkoxydim, cretodim, cyhalohop-butyl, quizalophop-ethyl, diclohop-methyl, clodinafop-propargylamide, phenoxapromamide Flufenacetate, picloram, prodiamine, phosamine-ammonium, 2,4-D, 2,4- B, dicamba, penoxthram, flumethoslam, napthalam, pendimethalin, oryzalin, MCPA (and its dimethylammonium, potassium and sodium salts), MCPA-isooctyl, MCPA-thioethylmecoprop, clopyralid, aminopyralide, triclopyr, fluoxypyr, diflufenzopyr , Imazapyr, imazetapyr, imazamakis, picolinaphene, oxyfluorfen, oxadiazone, carfentrazone-ethyl, sulfentrazone, flumioxazin, diflufenican, bromoxynyl, propanyl, thiobencarb, molinate, fluridone, mesotrione, sulcotrione, isoxaflutol , Isoxaben, clomazone, anilofos, beflubutamide, EnfreSate, Bentazone, Benzobicyclone, Benzophenap, Bromobutide, Butachlor, Butamifos, Caffentrol, Chlomeprop, Dimepiperate, Dimetamethrin, Diemron, Esprocarb, Etobenzanide, fentrazamide, fentrazamide, fentrazamide, fendrazamide ), Oxadichromemefone, oxadiargyl, pentoxazone, pyraclonyl, pyrazolate, pyributiccarb, pyriftalide, pyriminobac-methyl, tenylchlor, bispyribac-sodium, cleoxixidium, copper sulfate, synosulfuron, cyclosulfamuron, ethoxysulfuron, epoprodane, flucetosulfuron ,I Zosulfuron, metamihop, pyrazosulfuron-ethyl, quinchlorac, flucarbazone-sodium, propoxycarbazone-sodium, amicarbazone, florasulam, trisulfuron, triadifram, pinoxaden, tritosulfuron, amidosulfuron, metosram, sulfosulfuron, pyraflufen-ethyl, HOK Preferred is a mixture of a compound of the invention with a herbicide selected from the group consisting of -201, KUH-021 and CUH-35. Particularly preferred mixtures are selected from the following group (compound numbers refer to compounds in Index Tables AD): compound 4 and diuron; compound 9 and diuron; compound 58 and diuron; compound 64 and diuron; And their salts) and diuron; compound 94 and diuron; compound 95 (and their salts) and diuron; compound 96 and diuron;
Compound 4 and hexazinone; Compound 9 and hexazinone; Compound 58 and hexazinone; Compound 64 and hexazinone; Compound 65 (and their salts) and hexazinone; Compound 94 and hexazinone; Compound 95 (and their salts) Compound 96 and hexazinone; Compound 135 (and their salts) and Hexazinone; Compound 4 and terbacil; Compound 9 and terbacil; Compound 58 and terbacil; Compound 64 and terbacil; Compound 65 (and their salts) and terbacil; Compound 94 and terbacil; Compound 95 (and their salts) and terbacil; Compound 96 and terbacil; Compound 135 (and their salts) and terbacil; Compound 9 and Bromasil; Compound 58 and Bromacil; Compound 64 and Bromacil; Compound 65 (and their salts) and Bromacil; Compound 94 and Bromacil; Compound 95 (and their salts) and Bromacil; Compound 96 and Bromacil; Compound 135 (and their salts) and bromacil; Compound 4 and glyphosate; Compound 9 and glyphosate; Compound 58 and glyphosate; Compound 64 and glyphosate; Compound 65 (and their salts) and glyphosate; Compound 95 (and salts thereof) and glyphosate; Compound 96 and glyphosate; Compound 135 (and salts thereof) and glyphosate; Compound 4 and group Compound 9 and glufosinate; Compound 58 and glufosinate; Compound 65 (and their salts) and glufosinate; Compound 94 and glufosinate; Compound 95 (and their salts) and glufosinate; Compound 96 and glufosinate; Compound 135 (and salts thereof) and glufosinate; Compound 4 and azimusulfuron; Compound 9 and azimusulfuron; Compound 58 and azimusulfuron; Compound 64 and azimusulfuron; Compound 65 (and their salts) and azimusulfuron; Compound 95 (and their salts) and azimusulfuron; Compound 96 and azimusulfuron; Compound 135 (And their salts) and azimusulfuron; compound 4 and chlorsulfuron; compound 9 and chlorsulfuron; compound 58 and chlorsulfuron; compound 64 and chlorsulfuron; compound 65 (and their salts) and chlorsulfuron Compound 94 and chlorsulfuron; Compound 95 (and their salts) and chlorsulfuron; Compound 96 and chlorsulfuron; Compound 135 (and their salts) and chlorsulfuron; Compound 4 and etametsuflon-methyl; Compound 58 and etamethuron-methyl; Compound 64 and etamethuron-methyl; Compound 65 (and their salts) and etamethuron-methyl; Compound 94 and etamethuron-methyl; Compound 95 (and their salts) and etamethflon-methyl; Compound 96 and etamethflon-methyl; Compound 135 (and their salts) and etameflon-methyl; Compound 4 and chlorimuron-ethyl; Compound 9 and chlorimuron-ethyl; Compound 58 and Compound 64 and chlorimuron-ethyl; compound 65 (and their salts) and chlorimuron-ethyl; compound 94 and chlorimuron-ethyl; compound 95 (and their salts) and chlorimuron-ethyl; compound 96 and chlorimuron-ethyl Compound 135 (and their salts) and chlorimuron-ethyl; Compound 4 and bensulfuron-methyl; Compound 9 and bensulfuron-methyl; Compound 58 and bensulfuron Compound 64 and Bensulfuron-methyl; Compound 65 (and their salts) and Bensulfuron-methyl; Compound 94 and Bensulfuron-methyl; Compound 95 (and their salts) and Bensulfuron-methyl; Compound 96 and Benth Compound 135 (and salts thereof) and Bensulfuron-methyl; Compound 4 and rimsulfuron; Compound 9 and rimsulfuron; Compound 58 and rimsulfuron; Compound 64 and rimsulfuron; Compound 65 (and salts thereof) Compound 94 and rimsulfuron; Compound 95 (and their salts) and rimsulfuron; Compound 96 and rimsulfuron; Compound 135 (and their salts) and rimsulfuron;
Compound 9 and sulfometuron-methyl; Compound 58 and sulfometuron-methyl; Compound 64 and sulfometuron-methyl; Compound 65 (and their salts) and sulfometuron-methyl; Compound 94 and sulfometuron-methyl; Their salts) and sulfometuron-methyl; compound 96 and sulfometuron-methyl; compound 135 (and their salts) and sulfometuron—
Compound 4 and metsulfuron-methyl; Compound 9 and metsulfuron-methyl; Compound 58 and metsulfuron-methyl; Compound 64 and metsulfuron-methyl; Compound 65 (and their salts) and metsulfuron-methyl; Compound 94 and metsulfuron-methyl; Compound 95 (and their salts) and metsulfuron-methyl; Compound 96 and metsulfuron-methyl; Compound 135 (and their salts) and metsulfuron-methyl; Compound 4 and nicosulfuron; Compound 9 and nicosulfuron; Compound 58 and nicosulfuron Compound 64 and nicosulfuron; Compound 65 (and their salts) and nicosulfuron; Compound 94 and nicosulfuron; Compound 95 (and their salts) Compound 96 and nicosulfuron; Compound 135 (and their salts) and Nicosulfuron; Compound 4 and tribenuron-methyl; Compound 9 and tribenuron-methyl; Compound 58 and tribenuron-methyl; Compound 64 and tribenuron-methyl; Compound 65 (and their salts) and tribenuron-methyl; Compound 94 and tribenuron-methyl; Compound 95 (and their salts) and tribenuron-methyl; Compound 96 and tribenuron-methyl; Compound 135 (and their salts) and tribenuron Compound 4 and Thifensulfuron-methyl; Compound 9 and Thifensulfuron-methyl; Compound 58 and Thifensulfuron-methyl; Compound 64 and Thifensulfuron Compound 65 (and their salts) and Thifensulfuron-methyl; Compound 94 and Thifensulfuron-methyl; Compound 95 (and their salts) and Thifensulfuron-methyl; Compound 96 and Thifensulfuron-methyl Compound 135 (and salts thereof) and thifensulfuron-methyl; Compound 4 and flupylsulfuron-methyl; Compound 9 and flupylsulfuron-methyl; Compound 58 and flupylsulfuron-methyl; Compound 64 and flupirsulfuron- Compound 65 (and their salts) and flupirsulfuron-methyl; Compound 94 and flupylsulfuron-methyl; Compound 95 (and their salts) and flupylsulfuron-methyl; Compound 96 and flupirsulfur Compound 135 (and salts thereof) and flupirsulfuron-methyl; Compound 4 and flupylsulfuron-methyl-sodium; Compound 9 and flupylsulfuron-methyl-sodium; Compound 58 and flupirsulfuron-methyl- Compound 64 and flupirsulfuron-methyl-sodium; Compound 65 (and salts thereof) and flupylsulfuron-methyl-sodium; Compound 94 and flupylsulfuron-methyl-sodium; Compound 95 (and salts thereof) and Flupylsulfuron-methyl-sodium; Compound 96 and flupirsulfuron-methyl-sodium; Compound 135 (and their salts) and flupirsulfuron-methyl-sodium; Compound 4 and halosulfur Compound 9 and halosulfuron-methyl; Compound 58 and halosulfuron-methyl; Compound 64 and halosulfuron-methyl; Compound 65 (and their salts) and halosulfuron-methyl; Compound 94 and halosulfuron-methyl; Compound 95 (and their salts) and halosulfuron-methyl; Compound 96 and halosulfuron-methyl; Compound 135 (and their salts) and halosulfuron-methyl; Compound 4 and primsulfuron-methyl; Compound 9 and primis Compound 58 and Primsulfuron-methyl; Compound 64 and Primsulfuron-methyl; Compound 65 (and their salts) and Primsulfuron-methyl; Compound 94 and Primsulfuron-methyl; 95 (and their salts) and primsulfuron-methyl; Compound 96 and primsulfuron-methyl; Compound 135 (and their salts) and Primsulfuron-methyl; Compound 4 and trifluorosulfuron; Compound 9 and Trif Compound 58 and Trifloxysulfuron; Compound 64 and Trifloxysulfuron; Compound 65 (and their salts) and Trifloxysulfuron; Compound 94 and Trifloxysulfuron; Compound 95 (and their salts) Compound 96 and trifloxysulfuron; Compound 135 (and their salts) and trifloxysulfuron;
Compound 4 and Foramsulfuron; Compound 9 and Foramsulfuron; Compound 58 and Foramsulfuron; Compound 64 and Foramsulfuron; Compound 65 (and their salts) and Foramsulfuron; Compound 94 and Foramsulfuron; (And their salts) and foramsulfuron; compound 96 and foramsulfuron; compound 135 (and their salts) and foramsulfuron; compound 4 and mesosulfuron-methyl; compound 9 and mesosulfuron-methyl; compound 58 and mesosulfuron- Compound 64 and mesosulfuron-methyl; Compound 65 (and their salts) and mesosulfuron-methyl; Compound 94 and mesosulfuron-methyl; Compound 95 (and their salts) and mesosulfur Compound 96 and mesosulfuron-methyl; Compound 135 (and their salts) and mesosulfuron-methyl; Compound 4 and iodosulfuron-methyl; Compound 9 and iodosulfuron-methyl; Compound 58 and iodosulfuron-methyl Compound 64 and iodosulfuron-methyl; Compound 65 (and their salts) and iodosulfuron-methyl; Compound 94 and iodosulfuron-methyl; Compound 95 (and their salts) and iodosulfuron-methyl; 96 and iodosulfuron-methyl; compound 135 (and their salts) and iodosulfuron-methyl; compound 4 and isoproturon; compound 9 and isoproturon; compound 58 and isoproturon; Compound 65 (and their salts) and isoproturon; Compound 94 and isoproturon; Compound 95 (and their salts) and isoproturon; Compound 96 and isoproturon; Compound 135 (and their salts) and isoproturon; Compound 4 and amethrin; Compound 9 and amethrin; Compound 58 and amethrin; Compound 64 and amethrin; Compound 65 (and salts thereof) and amethrin; Compound 94 and amethrin; Compound 95 (and salts thereof) and amethrin; Compound 96 and amethrin; And their salts) and ametrine; compound 4 and amitrol; compound 9 and amitrol; compound 58 and amitrol; compound 64 and amitrol; (And their salts) and amitrol; Compound 94 and amitrol; Compound 95 (and their salts) and amitrol; Compound 96 and amitrol; Compound 135 (and their salts) and amitrol; Compound 4 and paraquat dichloride; Compound 58 and paraquat dichloride; Compound 64 and paraquat dichloride; Compound 65 (and salts thereof) and paraquat dichloride; Compound 94 and paraquat dichloride; Compound 95 (and salts thereof) and paraquat dichloride; Compound 96 and paraquat dichloride Compound 135 (and salts thereof) and paraquat dichloride; Compound 4 and diquat dibromide; Compound 9 and diquat dibromide Compound 58 and diquat dibromide; Compound 64 and diquat dibromide; Compound 65 (and salts thereof) and diquat dibromide; Compound 94 and diquat dibromide; Compound 95 (and salts thereof) and diquat dibromide; Compound 135 (and their salts) and Diquat dibromide; Compound 4 and atrazine; Compound 9 and atrazine; Compound 58 and atrazine; Compound 64 and atrazine; Compound 65 (and their salts) and atrazine; 94 and Atrazine; Compound 95 (and their salts) and Atrazine; Compound 96 and Atrazine; Compound 135 (and their salts) and Atrazine; Compound 4 and Metribuzin; Compound 58 and Metribuzin; Compound 64 and Metribuzin; Compound 65 (and their salts) and Metribuzin; Compound 94 and Metribuzin; Compound 95 (and their salts) and Metribuzin; Compound 96 and Metribuzin; Compound 4 and acetochlor; Compound 9 and acetochlor; Compound 58 and acetochlor; Compound 64 and acetochlor; Compound 65 (and their salts) and acetochlor; Compound 94 and acetochlor; Compound 95 (and their salts) Compound 96 and acetochlor; Compound 135 (and their salts) and acetochlor; Compound 4 and metolachlor; Compound 9 and metolak Compound 58 and metolachlor; Compound 64 and metolachlor; Compound 65 (and their salts) and metolachlor; Compound 94 and metolachlor; Compound 95 (and their salts) and metolachlor; Compound 96 and metolachlor; Compound 135 (and their Compound 4 and S-metolachlor; Compound 9 and S-metolachlor; Compound 58 and S-metolachlor; Compound 64 and S-metolachlor; Compound 65 (and their salts) and S-metolachlor; Compound 94 and S Compound 95 (and their salts) and S-metolachlor; Compound 96 and S-metolachlor; Compound 135 (and their salts) and S-metolachlor; Compound 4 and alachlor Compound 9 and alachlor; Compound 58 and alachlor; Compound 64 and alachlor; Compound 65 (and their salts) and alachlor; Compound 94 and alachlor; Compound 95 (and their salts) and alachlor; Compound 4 and pretilachlor; compound 9 and pretilachlor; compound 58 and pretilachlor; compound 64 and pretilachlor; compound 65 (and their salts) and pretilachlor; compound 94 and pretilachlor; compound 95 (and theirs) Compound 96 and pretilachlor; compound 135 (and their salts) and pretilachlor; compound 4 and cetoxidim; compound Compound 58 and cetoxidim; Compound 64 and cetoxidim; Compound 65 (and their salts) and cetoxidim; Compound 94 and cetoxidim; Compound 95 (and their salts) and cetoxidim; Compound 96 and cetoxidim; Compound 4 and tralcoxidim; Compound 9 and tralcoxidim; Compound 58 and tralcoxidim; Compound 64 and tralcoxidim; Compound 65 (and their salts); Compound 94 and tralcoxidium; Compound 95 (and their salts) Compound 96 and tralcoxizi; Compound 135 (and their salts) and tralcoxidim; Compound 4 and Compound 9 and cretodim; Compound 58 and cretodim; Compound 64 and cletodim; Compound 65 (and their salts); Compound 94 and cletodim; Compound 95 (and their salts) and cretodim; Compound 135 (and their salts) and cretodim; Compound 4 and cyhalohop-butyl; Compound 9 and cyhalohop-butyl; Compound 58 and cyhalohop-butyl; Compound 64 and cyhalohop-butyl; Compound 65 (and their salts) and cyhalohop- Compound 94 and sihalohop-butyl; Compound 95 (and their salts) and sihalohop-butyl; Compound 96 and sihalohop-butyl; Compound 135 (and their salts) and Shiha E-flops - butyl;
Compound 4 and quizalopop-ethyl; Compound 9 and quizalopop-ethyl; Compound 58 and quizalophop-ethyl; Compound 64 and xylohop-ethyl; Compound 65 (and their salts) and quizalopop-ethyl; (And their salts) and quizalop-ethyl; compound 96 and quizalop-ethyl; compound 135 (and their salts) and quisalop-ethyl; compound 4 and diclohop-methyl; compound 9 and diclohop-methyl; compound 58 and diclohop- Compound 64 and diclohop-methyl; Compound 65 (and their salts) and diclohop-methyl; Compound 94 and diclohop-methyl; Compound 95 (and their salts) and diclohop-meth Compound 96 and diclohop-methyl; Compound 135 (and their salts) and diclohop-methyl; Compound 4 and clodinaf-propargyl; Compound 9 and clodinaf-propargyl; Compound 58 and clodinahop-propargyl; Compound 64 and clodinahop-propargyl; Compound 94 (and their salts) and Clodinahop-propargyl; Compound 94 and Clodinahop-propargyl; Compound 95 (and their salts) and Clodinahop-propargyl; Compound 96 and Clodinahop-propargyl; Compound 135 (and their salts) and Clodinahop- Compound 4 and phenoxaprop-ethyl; Compound 9 and phenoxaprop-ethyl; Compound 58 and phenoxaprop- Compound 64 and phenoxaprop-ethyl; compound 65 (and their salts) and phenoxaprop-ethyl; compound 94 and phenoxaprop-ethyl; compound 95 (and their salts) and phenoxaprop-ethyl; compound 96 and phenoxaprop-ethyl; Compound (and salts thereof) and phenoxaprop-ethyl; Compound 4 and dimethenamide; Compound 9 and dimethenamide; Compound 58 and dimethenamide; Compound 64 and dimethenamide; Compound 65 (and their salts) and dimethenamide; Compound 94 and dimethenamide; (And their salts) and dimethenamide; Compound 96 and dimethenamide; Compound 135 (and their salts) and dimethenamide; Compound 4 and flufenacetate; Compound 9 and flufenaceto; Compound 58 and flufenaceto; Compound 64 and flufenacetate; Compound 65 (and their salts) and flufenacetate; Compound 94 and flufenacetate; (And their salts) and flufenacet; Compound 96 and flufenacetate; Compound 135 (and their salts) and flufenacetate; Compound 4 and picloram; Compound 9 and picloram; Compound 58 and picloram; Compound 65 (and their salts) and picloram; Compound 94 and picloram; Compound 95 (and their salts) and picloram; Compound 96 and picloram; Compound 135 (and their salts) and pic Compound 4 and prodiamine; Compound 9 and prodiamine; Compound 58 and prodiamine; Compound 64 and prodiamine; Compound 65 (and their salts) and prodiamine; Compound 94 and prodiamine; Compound 95 (and their Compound 96 and prodiamine; Compound 135 (and their salts) and prodiamine; Compound 4 and phosamine-ammonium; Compound 9 and phosamine-ammonium; Compound 58 and phosamine-ammonium; Compound 64 and phosamine- Compound 65 (and their salts) and phosamine-ammonium; Compound 94 and phosamine-ammonium; Compound 95 (and their salts) and phosamine-ammonium; Compound 96 and phosamine-ammonium; Compound 135 (and their salts) and phosamine-ammonium; Compound 4 and 2,4-D; Compound 9 and 2,4-D; Compound 58 and 2,4-D; Compound 65 (and their salts) and 2,4-D; Compounds 94 and 2,4-D; Compound 95 (and their salts) and 2,4-D; Compounds 96 and 2 , 4-D; compounds 135 (and their salts) and 2,4-D; compounds 4 and 2,4-DB; compounds 9 and 2,4-DB; compounds 58 and 2,4-DB; Compounds 65 (and their salts) and 2,4-DB; Compounds 94 and 2,4-DB; Compounds 95 (and their salts) and 2,4-DB; 96 and 2,4-DB; Compound 135 (and their salts) and 2,4-DB; Compound 4 and Dicamba; Compound 9 and Dicamba; Compound 58 and Dicamba; Compound 64 and Dicamba; Compound 65 (and their salts) Compound 94 and Dicamba; Compound 95 (and their salts) and Dicamba; Compound 96 and Dicamba; Compound 135 (and their salts) and Dicamba; Compound 4 and Penox slam; Compound 9 and Penox slam; Compound 58 and Penox slam Compound 64 and penox slam; Compound 65 (and their salts) and penox slam; Compound 94 and penox slam; Compound 95 (and their salts) and penox slam; Compound 96 and penox slam; 35 (and their salts) and penox slam; Compound 4 and flumethoslam; Compound 9 and flumethoslam; Compound 58 and flumethoslam; Compound 64 and flumethoslam; Compound 65 (and their salts) and flumethoslam; Compound 94 and flumethoslam; Compound 96 and flumethoslam; Compound 135 (and their salts) and flumethoslam; Compound 4 and naptalam; Compound 9 and naptalam; Compound 58 and naptalam; Compound 64 and naptalum; Compound 65 (and their salts) Compound 94 and Naptalam; Compound 95 (and their salts) and Naptalam; Compound 96 and Naptalam; Compound 135 Compound 4 and pendimethalin; compound 9 and pendimethalin; compound 58 and pendimethalin; compound 64 and pendimethalin; compound 65 (and their salts) and pendimethalin; compound 94 and pendimethalin; compound 95 (and theirs) Compound 96 and pendimethalin; compound 135 (and their salts) and pendimethalin; compound 4 and oryzalin; compound 9 and oryzalin; compound 58 and oryzalin; compound 64 and oryzalin; compound 65 (and their salts) and Compound 94 and oryzalin; compound 95 (and their salts) and oryzalin; compound 96 and oryzalin; compound 135 (and it) Compound 4 and MCPA (and their salts and (thio) esters); Compound 9 and MCPA (and their salts and (thio) esters); Compound 58 and MCPA (and their salts and ( Compound 64 and MCPA (and their salts and (thio) esters); Compound 65 (and their salts) and MCPA (and their salts and (thio) esters); Compound 94 and MCPA (and their) Compound 95 (and their salts) and MCPA (and their salts and (thio) esters); Compound 96 and MCPA (and their salts and (thio) esters); Compound 135 ( And their salts) and MCP (And their salts and (thio) esters); compound 4 and mecoprop; compound 9 and mecoprop; compound 58 and mecoprop; compound 64 and mecoprop; compound 65 (and their salts) and mecoprop; (And their salts) and mecoprop; compound 96 and mecoprop; compound 135 (and their salts) and mecoprop; compound 4 and clopyralide; compound 9 and clopyralide; compound 58 and clopyralide; compound 64 and clopyralide; Compound 94 and clopyralide; Compound 95 (and their salts) and clopyralide; Compound 96 and clopyralide; Compound 135 (and their salts) Compound 9 and aminopyralide; Compound 58 and aminopyralide; Compound 64 and aminopyralide; Compound 65 (and their salts) and aminopyralide; Compound 94 and aminopyralide; Compound 95 (and their salts) and aminopyralide; Compound 96 and aminopyralide; Compound 135 (and their salts) and aminopyralide; Compound 4 and triclopyr; Compound 9 and triclopyr; Compound 58 and triclopyr; Compound 64 and triclopyr; Compound 65 (and their salts) and triclopyr; Compound 95 (and their salts) and Triclopyr; Compound 96 and Triclopyr; Compound 135 (and them) Compound 4 and fluroxypyr; Compound 9 and fluroxypyr; Compound 58 and fluroxypyr; Compound 64 and fluroxypyr; Compound 65 (and their salts) and Fluroxypyr; Compound 94 and fluroxypyr; Compound 95 (and their salts) Compound 96 and fluroxypyr; Compound 135 (and their salts) and fluroxypyr; Compound 4 and diflufenzopyr; Compound 9 and diflufenzopyr; Compound 58 and diflufenzopyr; Compound 64 and diflufenzopyr Compound 65 (and their salts) and diflufenzopyr; Compound 94 and diflufenzopyr; Compound 95 (and their salts) and diflufenzopyr; 6 and diflufenzopyr; compound 135 (and their salts) and diflufenzopyr; compound 4 and imazapyr; compound 9 and imazapyr; compound 58 and imazapyr; compound 64 and imazapyr; compound 65 (and their salts) and Imazapyr; Compound 94 and Imazapyr; Compound 95 (and it
Compound 96 and Imazapyr; Compound 135 (and their salts) and Imazapyr; Compound 4 and Imazetapyr; Compound 9 and Imazetapyr; Compound 58 and Imazetapyr; Compound 64 and Imazetapyr; Compound 65 (and their salts) Compound 94 and imazetapil; Compound 95 (and their salts) and imazetapyr; Compound 96 and imazetapyr; Compound 135 (and their salts) and imazetapyr; Compound 4 and imazamox; Compound 9 and imazamox; Compound 58 and imazamox Compound 64 and imazamokiss; Compound 65 (and their salts) and imazamokiss; Compound 94 and imazamokiss; Compound 95 (and their salts) and Compound 96 and imazamokiss; Compound 135 (and their salts) and imazamokiss; Compound 4 and picolinaphene; Compound 9 and picolinaphene; Compound 58 and picolinaphene; Compound 64 and picolinaphene; Compound 65 (and their salts) and picolinaphene; 94 and picolinaphene; compound 95 (and their salts) and picolinaphene; compound 96 and picolinaphene; compound 135 (and their salts) and picolinaphene; compound 4 and oxyfluorfen; compound 9 and oxyfluorfen; compound 58 and oxyfluorfen; 64 and oxyfluorphene; compound 65 (and their salts) and oxyfluorfen; compound 94 and oxy Compound 95 (and salts thereof) and oxyfluorfen; Compound 96 and oxyfluorfen; Compound 135 (and salts thereof) and oxyfluorfen; Compound 4 and oxadiazone; Compound 9 and oxadiazone; Compound 58 and oxadiazone; Compound 65 (and their salts) and oxadiazone; Compound 94 and oxadiazone; Compound 95 (and their salts) and oxadiazone; Compound 96 and oxadiazone; Compound 135 (and their salts) and oxadiazone; Compound 9 and carfentrazone-ethyl; Compound 58 and carfentrazone-ethyl; Compound 64 and calf Compound 65 (and their salts) and carfentrazone-ethyl; Compound 94 and carfentrazone-ethyl; Compound 95 (and their salts) and carfentrazone-ethyl; Compound 96 and cal Compound 135 (and salts thereof) and carfentrazone-ethyl; Compound 4 and sulfentrazone; Compound 9 and sulfentrazone; Compound 58 and sulfentrazone; Compound 64 and sulfentrazone Compound 65 (and their salts) and sulfentrazone; Compound 94 and sulfentrazone; Compound 95 (and their salts) and sulfentrazone; Compound 96 and sulfentrazone; Compound 135 (And their salts) and Compound 4 and flumioxazin; Compound 9 and flumioxazin; Compound 58 and flumioxazin; Compound 64 and flumioxazin; Compound 65 (and their salts) and flumioxazin; Compound 94 and flumioxazin; Compound 96 and flumioxazin; compound 135 (and their salts) and flumioxazin; compound 4 and diflufenican; compound 9 and diflufenican; compound 58 and diflufenican; compound 64 and diflufenican; And their salts) and diflufenican; Compound 94 and diflufenican; Compound 95 (and their salts) and diflufenican; Compound 135 (and their salts) and diflufenican; Compound 4 and bromoxynyl; Compound 9 and bromoxynyl; Compound 58 and bromoxynil; Compound 64 and bromoxynil; Compound 65 (and their salts) and bromoxynil; Compound 95 (and their salts) and bromoxynil; Compound 96 and bromoxynyl; Compound 135 (and their salts) and bromoxynil; Compound 4 and propanyl; Compound 9 and propanyl; Compound 58 and propanil; (And their salts) and propanil; compound 94 and propanil; compound 95 (and their salts) and propanil; compound 96 and propanil; compound 135 (and their salts) and propanil; compound 4 and thiobencarb; compound 9 and thiobencarb; compound 58 and thiobencarb; compound 64 and thiobencarb; compound 65 (and their salts) and thiobencarb; Compound 95 (and their salts) and thiobencarb; Compound 96 and thiobencarb; Compound 135 (and their salts) and thiobencarb; Compound 4 and fluridone; Compound 9 and fluridone; Compound 58 and fluridone; (And their salts) and fluridone; compound 94 and fluridone; compound 95 (and their salts) and fluridone; compound 96 and Compound 135 (and their salts) and fluridone; Compound 4 and mesotrione; Compound 9 and mesotrione; Compound 58 and mesotrione; Compound 64 and mesotrione; Compound 65 (and their salts) and mesotrione; 95 (and their salts) and mesotrione; Compound 96 and mesotrione; Compound 135 (and their salts) and mesotrione; Compound 4 and sulcotrione; Compound 9 and sulcotrione; Compound 58 and sulcotrione; Compound 65 (and their salts) and sulcotrione; Compound 94 and sulcotrione; Compound 95 (and their salts) and sulcotrione; Compound 96 and Compound 135 (and salts thereof) and sulcotrione; Compound 4 and isoxaflutol; Compound 9 and isoxaflutol; Compound 58 and isoxaflutol; Compound 64 and isoxaflutol; Compound 65 (and Compound 94 and isoxaflutol; Compound 95 (and their salts) and isoxaflutol; Compound 96 and isoxaflutol; Compound 135 (and their salts) and Compound 4 and isoxaben; compound 9 and isoxaben; compound 58 and isoxaben; compound 64 and isoxaben; compound 65 (and their salts) and isoxaben; compound 94 and isoxaben; compound 95 (and so on) Compound 96 and isoxaben; Compound 135 (and their salts) and Isoxaben; Compound 4 and clomazone; Compound 9 and clomazone; Compound 58 and clomazone; Compound 64 and clomazone; Compound 65 (and their Compound 94 and clomazone; Compound 95 (and salts thereof) and clomazone; Compound 96 and clomazone; Compound 135 (and salts thereof) and clomazone; Compound 4 and beflubutamide; Compound 9 and beflubutamide; Compound 58 and Compound 64 and beflubutamide; Compound 65 (and their salts) and beflubutamide; Compound 94 and beflubutamide; Compound 95 (and their salts) and Compound 96 and beflubutamide; Compound 135 (and salts thereof) and beflubutamide; Compound 4 and benfrecetate; Compound 9 and benfrecetate; Compound 58 and benfrecetate; Compound 64 and benfrecetate; Compound 95 (and salts thereof) and Benfresate; Compound 96 and Benfresate; Compound 135 (and salts thereof) and Benfrateate; Compound 4 and Bentazone; Compound 9 and Bentazone; Compound 58 and Bentazone; Compound 65 (and their salts) and bentazone; Compound 94 and bentazone; Compound 95 (and their salts) and Compound 96 and Bentazone; Compound 135 (and their salts) and Bentazone; Compound 4 and benzobicyclone; Compound 9 and benzobicyclone; Compound 58 and benzobicyclone; Compound 64 and benzobicyclone; Compound 94 and benzobicyclone; Compound 95 (and their salts) and benzobicyclone; Compound 96 and benzobicyclone; Compound 135 (and their salts) and benzobicyclone; Compound 9 and benzophenap; Compound 58 and benzophenap; Compound 64 and benzophenap; Compound 65 (and their salts) and benzophenap; Compound 94 and benzophenap;
Compound 95 (and their salts) and benzophenap; Compound 96 and benzophenap; Compound 135 (and their salts) and benzophenap; Compound 4 and bromobutide; Compound 9 and bromobutide; Compound 58 and bromobutide; Compound 64 and bromobutide; Compound 94 and bromobutide; Compound 95 (and their salts) and bromobutide; Compound 96 and bromobutide; Compound 135 (and their salts) and bromobutide; Compound 4 and butachlor; Compound 9 and butachlor; Compound 58 and Butachlor; Compound 64 and Butachlor; Compound 65 (and their salts) and Butachlor; Compound 94 and Butachlor; Compound 95 (and its Compound 96 and Butachlor; Compound 135 (and their salts) and Butachlor; Compound 4 and Cavenstrol; Compound 9 and Cavenstrol; Compound 58 and Cavenstrol; Compound 64 and Cavenstrol; Compound 65 (and their salts) Compound 94 and Caffentrol; Compound 95 (and their salts) and Cavenstrol; Compound 96 and Cavenstrol; Compound 135 (and their salts) and Cavenstrol; Compound 4 and Chromprop; Compound 9 and Chromprop; Compound 58 and Chromprop Compound 64 and chromeprop; Compound 65 (and their salts) and chromeprop; Compound 94 and Compound 95 (and their salts) and chromeprop; Compound 96 and chromeprop; Compound 135 (and their salts) and chromeprop; Compound 4 and dimethylpiperate; Compound 9 and dimethylpiperate; Compound 58 and dimethylpiperate; Compound 64 and dimepiperate; Compound 65 (and their salts) and dimethylpiperate; Compound 94 and dimethylpiperate; Compound 95 (and their salts) and dimethylpiperate; Compound 96 and dimethylpiperate; Compound 135 (and their salts) and dimethylpiperate; Compound 4 and dimetamethrin; Compound 58 and dimetamethrin; Compound 64 and dimetamethrin; Compound 65 (and their salts) and dimetametry Compound 94 and dimetamethrin; Compound 95 (and their salts) and dimetamethrin; Compound 96 and dimetamethrin; Compound 135 (and their salts) and dimetamethrin; Compound 4 and diamuron; Compound 9 and diamtron; Compound 64 and Diamron; Compound 65 (and their salts) and Diamron; Compound 94 and Diamron; Compound 95 (and their salts) and Diamron; Compound 96 and Diamron; Compound 135 (and their salts) and Diamron; Compound 4 and Esprocarb; Compound 9 and Esprocarb; Compound 58 and Esprocarb; Compound 64 and Esprocarb; Compound 65 (and their salts) and E Compound 94 and Esprocarb; Compound 95 (and their salts) and Esprocarb; Compound 96 and Esprocarb; Compound 135 (and their salts) and Esprocarb; Compound 4 and Etobenzanide; Compound 9 and Etobenzanide; Compound 58 and Etobenzanide; Compound 65 (and their salts) and Etobenzanide; Compound 94 and Etobenzanide; Compound 95 (and their salts) and Etobenzanide; Compound 96 and Etobenzanide; Compound 135 (and their salts) and Etobenzanide; Compound 9 and Fentrazamide; Compound 58 and Fentrazamide; Compound 64 and Compound 65 (and their salts) and Fentrazamide; Compound 94 and Fentrazamide; Compound 95 (and their salts) and Fentrazamide; Compound 96 and Fentrazamide; Compound 135 (and their Compound 4 and indanophan; compound 58 and indanophan; compound 64 and indanophan; compound 65 (and salts thereof) and compound 65 and indanophan; compound 94 and indanophan; compound 95 (and salts thereof) ) And indanophan; compound 96 and indanophan; compound 135 (and their salts) and indanophan; compound 4 and cumyluron; compound 9 and cumyluron; 58 and cumyluron; compound 64 and cumyluron; compound 65 (and their salts) and cumyluron; compound 94 and cumyluron; compound 95 (and their salts) and cumyllon; compound 96 and cumyluron; compound 135 (and their salts) and Compound 4 and mefenacet; compound 9 and mefenacet; compound 58 and mefenacet; compound 64 and mefenacet; compound 65 (and their salts) and mefenacet; compound 94 and mefenacet; compound 95 (and their salts) and mefenacet; 96 and mefenacet; compound 135 (and their salts) and mefenacet; compound 4 and oxadiclomephone; compound 9 and oxadiclomefo Compound 58 and oxadichromemefone; Compound 64 and oxadichromephone; Compound 65 (and their salts) and oxadichromemefone; Compound 94 and oxadichromephone; Compound 95 (and their salts) and oxadi Compound 96 and oxadichlormephone; Compound 135 (and their salts) and oxadiclomephone; Compound 4 and oxadiargyl; Compound 9 and oxadiargyl; Compound 58 and oxadiargyl; Compound 64 and oxadiargyl; Compound 94 and Oxadiargyl; Compound 95 (and their salts) and Oxadiargyl; Compound 96 and Oxadiargyl; Compound 135 (and them) Compound 4 and pentoxazone; Compound 58 and pentoxazone; Compound 64 and pentoxazone; Compound 65 (and their salts) and Compound 94 and pentoxazone; Compound 95 (and their salts) and Compound 96 and pentoxazone; Compound 135 (and their salts) and Pentoxazone; Compound 4 and pyraclonyl; Compound 9 and pyraclonyl; Compound 58 and pyraclonyl; Compound 64 and pyraclonyl; Compound 65 (and their salts) and pyraclonyl; 94 and pyraclonyl; Compound 95 (and their salts) and pyraclonyl; Compound 96 and pyraclonyl; Compound 4 and pyrazolate; Compound 58 and pyrazolate; Compound 64 and pyrazolate; Compound 65 (and their salts) and pyrazolate; Compound 94 and pyrazolate; Compound 95 (and their Compound 96 and pyrazolate; Compound 135 (and their salts) and pyrazolate; Compound 4 and pyributycarb; Compound 9 and pyributycarb; Compound 58 and pyributycarb; Compound 64 and pyributycarb; Compound 65 (and their salts) and Compound 94 and pyributicalb; Compound 95 (and their salts) and pyributicalb; Compound 96 and pyributicalbu; Compound 13 Compound 4 and pyriftalide; Compound 9 and pyriftalide; Compound 58 and pyriftalide; Compound 64 and pyriftalide; Compound 65 (and their salts) and pyriftalide; Compound 94 and pyriftalide; Compound 95 (and their Compound 96 and pyriftalide; Compound 135 (and their salts) and pyriftalide; Compound 4 and pyriminobac-methyl; Compound 9 and pyriminobac-methyl; Compound 58 and pyriminobac-methyl; Compound 64 and pyriminobac-methyl; Compound 65 (and salts thereof) and pyriminobac-methyl; Compound 94 and pyriminobac-methyl; Compound 95 (and salts thereof) and pyriminobac- Compound 96 and pyriminobac-methyl; compound 135 (and salts thereof) and pyriminobac-methyl; compound 4 and tenyl chlor; compound 9 and tenyl chlor; compound 58 and tenyl chlor; compound 64 and tenyl chlor; compound 65 (and their salts) Compound 94 and Tenyl Chlor; Compound 95 (and their salts) and Tenyl Chlor; Compound 96 and Tenyl Chlor; Compound 135 (and their salts) and Tenyl Chlor; Compound 4 and Bispyribac-Sodium; Compound 9 and Bispyribac-Sodium; 58 and bispyribac-sodium; compound 64 and bispyribac-sodium; compound 65 (and their salts) and bispyribac-sodium; compound 9
Compound 95 (and their salts) and Bispyribac-sodium; Compound 96 and Bispyribac-sodium; Compound 135 (and their salts) and Bispyribac-sodium; Compound 4 and cleoxidim; Compound 9 and cleoxidim; 58 and cleoxidim; compound 64 and cleoxidim; compound 65 (and their salts) and cleoxydim; compound 94 and cleoxidim; compound 95 (and their salts) and cleoxidim; compound 96 and cleoxidim; compound 135 (and their salts) and Compound 4 and Cinosulfuron; Compound 9 and Cinosulfuron; Compound 58 and Cinosulfuron; Compound 64 and Cinosulfuron Compound 65 (and their salts) and synosulfuron; Compound 94 and sinosulfuron; Compound 95 (and their salts) and synosulfuron; Compound 96 and synosulfuron; Compound 135 (and their salts) and synosulfuron; Compound 4 and cyclosulfurone Compound 9 and cyclosulfamuron; Compound 58 and cyclosulfamuron; Compound 64 and cyclosulfamuron; Compound 65 (and their salts) and cyclosulfamlone; Compound 94 and cyclosulfamuron; 95 (and their salts) and cyclosulfamlone; Compound 96 and cyclosulfamlone; Compound 135 (and their salts) and cyclosulfamlone; Compound 4 and ethoxysulfuron; 9 and ethoxysulfuron; compound 58 and ethoxysulfuron; compound 64 and ethoxysulfuron; compound 65 (and their salts) and ethoxysulfuron; compound 94 and ethoxysulfuron; compound 95 (and their salts) and ethoxy Compound 96 and ethoxysulfuron; Compound 135 (and salts thereof) and ethoxysulfuron; Compound 4 and epoprodan; Compound 9 and epoprodan; Compound 58 and epoprodan; Compound 64 and epoprodan; Compound 65 (and salts thereof) ) And epoprodan; Compound 94 and epoprodan; Compound 95 (and their salts) and epoprodan; Compound 96 and epoprodan; Compound 135 (and their salts) and epoprod Compound 4 and flucetosulfuron; Compound 9 and flucetosulfuron; Compound 58 and flucetosulfuron; Compound 64 and flucetosulfuron; Compound 65 (and their salts) and flucetosulfuron; Compound 94 and flucetosulfuron; Compound 95 (and their salts) and flucesulfuron; Compound 96 and flucesulfuron; Compound 135 (and their salts) and flucesulfuron; Compound 4 and imazosulfuron; Compound 9 and imazosulfuron; Compound 58 and imazosulfuron; Compound 65 (and salts thereof) and imazosulfuron; Compound 94 and imazosulfuron; Compound 95 (and salts thereof) and imazosulfuron; Compound 135 (and their salts) and Imazosulfuron; Compound 4 and Metamihop; Compound 9 and Metamihop; Compound 58 and Metamihop; Compound 64 and Metamihop; Compound 65 (and their salts) and Metamihop; Compound 94 and Metamihop Compound 95 (and their salts) and metamihop; Compound 96 and metamihop; Compound 135 (and their salts) and metamihop; Compound 4 and pyrazosulfuron-ethyl; Compound 9 and pyrazosulfuron-ethyl; Compound 58 and pyrazosulfuron-ethyl; Compound 65 (and their salts) and pyrazosulfuron-ethyl; Compound 94 and pyrazosulfuron-ethyl; 95 (and their salts) and pyrazosulfuron-ethyl; Compound 96 and pyrazosulfuron-ethyl; Compound 135 (and their salts) and pyrazosulfuron-ethyl; Compound 4 and quinchlorac; Compound 9 and quinchlorac; Compound 58 and quinchlorac; Compound 65 (and their salts) and quinchlorac; Compound 94 and quinchlorac; Compound 95 (and their salts) and quinchlorac; Compound 96 and quinchlorac; Compound 135 (and their salts) and quinchlorac; Compound 9 and flucarbazone-sodium; Compound 58 and flucarbazone-sodium; Compound 64 and flucarbazone-sodium; Compound 65 (and their salts) and flucarbazone-sodium; Compound 94 and flucarbazone-sodium; Compound 95 (and their salts) and flucarbazone-sodium; Compound 96 and flucarbazone-sodium; Compound 4 and propoxycarbazone-sodium; Compound 9 and propoxycarbazone-sodium; Compound 58 and propoxycarbazone-sodium; Compound 64 and propoxycarbazone-sodium; Compound 65 (and their salts) and propoxycarba Compound 94 and propoxycarbazone-sodium; Compound 95 (and their salts) and propoxycarbazone-sodium; Compound 96 and propoxycarbazone-sodium; Compound 135 (and their salts) and propoxycarbazone-sodium; Compound 4 and amicarbazone; Compound 9 and amicarbazone; Compound 58 and amicarbazone; Compound 64 and amicarbazone; Compound 95 and amicarbazone; Compound 96 and amicarbazone; Compound 135 (and their salts) and amicarbazone; Compound 4 and florasulam; Compound 9 and florasulam; Compound 58 and amicarbazone; Compound 64 and Flora slam; Compound 65 (and salts thereof) and Flora slam; Compound 94 and Flora slam; Compound 95 (and their salts) and florasuram; Compound 96 and florasuram; Compound 135 (and their salts) and florasuram; Compound 4 and trisulfuron; Compound 9 and trisulfuron; Compound 58 and trisulfuron; Compound 64 and trisulfuron; Compound 65 (and their salts) and trisulfuron; Compound 94 and trisulfuron; Compound 95 (and their salts) and trisulfuron; Compound 96 and trisulfuron; Compound 135 (and their salts) and trisulfuron; Compound 9 and triadifram; Compound 58 and triadifram; Compound 64 and triadifram; Compound 65 (and their salts) and triadifram; Compound 94 and triadifram; Compound 95 (and their salts) and triadifram; Compound 96 and triadifram; Compound 135 (and their salts) and triadifram; Compound 4 and pinoxadene; Compound 9 and pinoxadene; Compound 58 and pinoxadene; Compound 65 (and their salts) and Pinoxaden; Compound 94 and Pinoxaden; Compound 95 (and their salts) and Pinoxaden; Compound 96 and Pinoxaden; Compound 135 (and their salts) and Pinoxaden;
Compound 4 and tritosulfuron; compound 9 and tritosulfuron; compound 58 and tritosulfuron; compound 64 and tritosulfuron; compound 65 (and their salts) and tritosulfuron; compound 94 and tritosulfuron; (And their salts) and tritosulfuron; compound 96 and tritosulfuron; compound 135 (and their salts) and tritosulfuron; compound 4 and amidosulfuron; compound 9 and amidosulfuron; compound 58 and amidos Compound 64 and amidosulfuron; Compound 65 (and salts thereof) and amidosulfuron; Compound 94 and amidosulfuron; Compound 95 (and salts thereof) and amidosulfuron; Compound 96 and amidosulfuron Compound 135 (and salts thereof) and amidosulfuron; Compound 4 and methoslam; Compound 9 and methoslam; Compound 58 and methoslam; Compound 64 and methoslam; Compound 65 (and their salts) and methoslam; Compound 95 (and their salts) and methoslam; Compound 96 and methoslam; Compound 135 (and their salts) and methotram; Compound 4 and sulfosulfuron; Compound 9 and sulfosulfuron; Compound 58 and sulfosulfuron; Compound 65 (and salts thereof) and sulfosulfuron; Compound 94 and sulfosulfuron; Compound 95 (and salts thereof) and sulfosulfuron; Compound 96 and sulfosulfuron; Compound 135 (and salts thereof) and sulfosulfuron; Compound 4 and pyraflufen-ethyl; Compound 9 and pyraflufen-ethyl; Compound 58 and pyraflufen-ethyl; Compound 64 and pyraflufen-ethyl; Compound 65 (and salts thereof) Compound 94 and pyraflufen-ethyl; Compound 95 (and their salts) and pyraflufen-ethyl; Compound 96 and pyraflufen-ethyl; Compound 135 (and their salts) and pyraflufen-ethyl; Compound 4 and HOK -201; Compound 9 and HOK-201; Compound 58 and HOK-201; Compound 64 and HOK-201; Compound 65 (and their salts) and HOK-201; Compound 94 and HOK-201; Compound 95 (and their salts) and HOK-201; Compound 96 and HOK-201; Compound 135 (and their salts) and HOK-201; Compound 4 and KUH-021; KUH-021; Compound 58 and KUH-021; Compound 64 and KUH-021; Compound 65 (and their salts) and KUH-021; Compound 94 and KUH-021; Compound 95 (and their salts) and KUH-021 Compound 96 and KUH-021; Compound 135 (and their salts) and KUH-021; Compound 4 and CUH-35; Compound 9 and CUH-35; Compound 58 and CUH-35; Compound 64 and CUH-35; 65 (and their salts) and C H-35; compound 94 and CUH-35; compound 95 (and salts thereof) and CUH-35; compound 96 and CUH-35; compound 135 (and salts thereof) and CUH-35. The ratio of the compound of the present invention to other herbicidal active ingredients in the herbicidal composition is generally from 100: 1 to 1: 100, more commonly from 10: 1 to 1:10, and most commonly by weight. The ratio is 5: 1 to 1: 5. One skilled in the art can easily determine the optimal ratio based on the desired weed control range.

  Due to the greater additive (ie, synergistic) efficacy in certain weeds, a mixture of the compounds of the present invention and an auxin transport inhibitor (phytotropins) is particularly noteworthy, for example compound 1 (6 -Ethyl amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate) and diflufenzopyr. An auxin transport inhibitor is a chemical substance that suppresses auxin transport in plants by binding to, for example, an auxin carrier protein. Other examples of auxin transport inhibitors include naptalam (also known as N- (1-naphthyl) phthalamic acid and 2-[(1-naphthalenylamino) carbonyl] benzoic acid), 9-hydroxyfluorene- Examples include 9-carboxylic acid and 2,3,5-triiodobenzoic acid. Accordingly, an aspect of the present invention relates to a herbicidal mixture comprising a synergistically effective amount of the compound of claim 1 and an auxin transport inhibitor. A synergistically effective amount of an auxin transport inhibitor with a compound of the invention can be readily determined.

  The compounds of the present invention may also be added to benoxacor, BCS (1-bromo-4-[(chloromethyl) sulfonyl] benzene), cloquintocet-mexyl (cloquintocet-) to increase safety for certain crops. mexyl), cimetrinil, dichlormid, 2- (dichloromethyl) -2-methyl-1,3-dioxolane (MG191), fenchlorazole-ethyl, fenchlorim, flurazole ), Fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-ethyl, meso In combination with herbicide safeners such as xylphenone ((4-methoxy-3-methylphenyl) (3-methylphenyl) methanone), naphthalic anhydride (1,8-naphthalic anhydride) and oxabetrilin Can be used. An effective amount of a herbicide safener can be applied at the same time as the compound of the present invention or as a seed treatment. Accordingly, an aspect of the present invention relates to a herbicidal mixture comprising an effective palliative amount of a compound of the present invention and a herbicide safener. Seed treatment is particularly useful for selective weed control because it physically limits toxicity mitigation for crop plants. Thus, a particularly useful embodiment of the present invention comprises contacting the crop location with a herbicidally effective amount of a compound of the present invention, wherein the seed on which the crop grows is a safening effective amount of the safener. For selectively inhibiting undesirable vegetation growth in crops. The effective amount of safening of the safener can be readily determined by one of ordinary skill in the art through simple experimentation.

The compounds of the present invention, Abigurishin (aviglycine), N- (phenylmethyl)-1H-purin-6-amine, Epokoreon (epocholeone), gibberellins acid, gibberellins _{A 4} and _{A 7,} Harbin (harpin) proteins, main peak Plant growth regulators such as coat chloride, prohexadione calcium, prohydrojasmon, sodium nitrophenolate and trinexapac-methyl, and plants such as Bacillus cereus strain BP01 It can also be used in combination with growth-changing organisms.

The following tests demonstrate the inhibitory efficacy of the compounds of the present invention against specific weeds. However, the weed suppression obtained by the compounds is not limited to these types. See Index Tables AD for compound descriptions. The following abbreviations are used in the index table: t means tertiary, s means secondary, n means normal, i means iso, c means cyclo, Me means methyl, Et means ethyl. Meaning, Pr means propyl, i-Pr means isopropyl, Bu means butyl, Ph means phenyl, MeO means methoxy, EtO means ethoxy and CN means Means cyano. " ^, " Means a negative formal charge, and

Means a positive formal charge. The abbreviation “dec.” Indicates that the compound appears to decompose upon melting. The abbreviation “Ex.” Stands for “Example” followed by a number indicating the example in which the compound is prepared.

Biological Example of the Invention Test A
Barnyardgrass (barnyardgrass) (Echinochloa crus-galli), crabgrass (crabgrass) (Dgitaria sanguinalis), giant foxtail (giant foxtail) (Setaria faberi), morningglory (morningglory) (Ipomoea spp.), Pigweed (redroot pigweed) (Amaranthus retroflexus) and Directed soil spray (directed) using test chemicals planted in a blend of lobe soil and sand and seeded with a non-phytotoxic solvent mixture containing surfactants (soil spray) Therefore, it was treated before germination. At the same time, these seeds were treated by a post-emergence application of a similarly formulated test chemical.

  For post-emergence treatment, plants ranged in height from 2 cm to 10 cm and were in the 1-2 leaf stage. Treated plants and untreated controls were kept in the greenhouse for about 10 days, after which all treated plants were visually assessed for damage compared to untreated controls. The plant response assessments summarized in Table A are based on a scale of 0-100, with 0 being ineffective and 100 being complete suppression. A dash (-) response means no test result.

Test B
Echinochloa crus-galli, Surinam grass (Brachiaria decumbens), cocklebur (Xanthium sturumum), corn (Zea mais) (Lambsquarters) (Chenopodium album), morning glory (Ipomoea c)
planted with seeds selected from occinea, Amaranthus retroflexus, Abutilon theophrasti and wheat (Triticum aestivum) and formulated in a non-phytotoxic solvent mixture containing a surfactant Pre-emergence treatment.

  At the same time, plants selected from these crops and weed species, as well as Alasculus myosuroides and wild oats (Avena fatua), were treated by post-emergence application of similarly formulated test chemicals. For post-emergence treatment, the plants ranged in height from 2 cm to 18 cm (1-4 leaf stage). Plant species in the paddy field test include rice (Oryza sativa), umbrella sedge (Cyperus difformis), ducks salad (Heteranthera limosa) and rice grown to the second leaf stage for testing. Echinochloa crus-galli). Treated plants and controls were kept in the greenhouse for 13-15 days, after which all species were visually assessed compared to controls. The plant response assessments summarized in Table B are based on a scale of 0-100, with 0 being ineffective and 100 being complete suppression. A dash (-) response means no test result.

Test C
Bermudagrass (Cyonodon dactylon), Surinamegrass (Brachiaria decumbens), Xanthium sturumium, Zea mays, Digis (Digi)
taria sanguinalis), woolly cup glass (woolly cupgrass) (Eriochloa villosa), giant foxtail (Setaria faberii), goosegrass (goosegrass) (Eleusine indica), Johnson grass (johnsongrass) (Sorghum halepense), Kokia (kochia) (Kochia scoparia), Shiroza (Chenopodium album), morning glory (Ipomoea coccinea), eastern black nightshade (Solanum ptycanthum), yellow ginger (Cirrus nutsedp) esculentus, Amaranthus retroflexus, common ragweed (Ambrosia elatior), soybean (Glycine max), sunflower (commonly sewed) Plant seeds or small nuts were planted and pre-emergence treated with test chemicals formulated in a non-phytotoxic solvent mixture containing surfactant.

  At the same time, plants selected from these crops and weed species, as well as barley (Hordeum vulgare), Alopecurus myoloides, Canary grass (Canary grass) by post-emergence application of several similarly formulated test agents canarygrass (Phalaris minor), chickweed (Stellaria media, timber um (um) irum (bulmus tec), green foxtail (green)estivum), it was treated oat (Avena fatua) and window glass (windgrass) (Apera spica-venti). For post-emergence treatment, the plants ranged in height from 2 cm to 18 cm (1-4 leaf stage). Plant species in the paddy field test consisted of rice (Oryza sativa), umbrella sedge (Hyperanthera limosa) and Echinochloa crus-galli that grew to the second leaf stage for the test. Treated plants and controls were kept in the greenhouse for 12-14 days, after which all species were visually assessed compared to controls. The plant response assessments summarized in Table C are based on a scale of 0-100, with 0 being ineffective and 100 being complete suppression. A dash (-) response means no test result.

Test D
Catchweed bedstraw (galium; Galium)
aparine), chickweed (common chickweed) (Stellaria media), Kokia (Kochia scoparia), common lambsquarters (Chenopodium album), pigweed (Amaranthus retroflexus), Russian thistle (Russian thistle) (Salsola kali), wild buckwheat (wild buckwheat) (Polygonum convolvulus ), Wild mustard (Sinapis avenvensis), barley (Hordeum vulgare) and wheat (Triti).
seeds of plant species selected from (Cum aestivum) were planted and pre-emergence treated with test chemicals formulated in a non-phytotoxic solvent mixture containing surfactant.

  At the same time, plants selected from these crops and weed species were treated by post-emergence application of several test agents formulated in the same way. For post-emergence treatment, the plants ranged in height from 2 cm to 18 cm (1-4 leaf stage). Treated plants and controls were kept in a controlled growth environment for 15-25 days, after which all species were visually assessed compared to controls. The plant response assessments summarized in Table D are based on a scale of 0-100, with 0 being ineffective and 100 being complete suppression. A dash (-) response means no test result.

Test E
Three plastic bowls (about 16 cm in diameter) per evaluation, sterilized Tama silt soil with 35:50:15 ratio of sand, silt and clay, and 2.6% organic matter Was partially filled. The three pots planted individually were as follows. For each evaluation, the United States of America, Heteranthera limosa, smallflower umbrella sedge (Cyperus difformis), and purple butterfly (purple)
seeds from redstem) (Ammania coccinea) were planted in one 16 cm pot. For each evaluation, seeds of rice from 9 rice flats (Cyperus iria), beared (brdd.) Slangpletop (Leptochloa fusca ssp. A stand (Oryza sativa cv. “Japonica-M202”) and one stand of 6 transplanted rice seedlings (Oryza sativa cv. “Japonica-M202”) were planted in one 16 cm pot. For each evaluation,
Echinochloa crus-galli, rate watergrass (Echinochloa oryzicola), early watergrass (on), Elochlo oryzoids (e) and seeds of echinochlo oryzoids (e) Planted in a pot. Planting was continuously carried out so that the crop and weed species were in the 2.0-2.5 leaf stage at the time of treatment.

  Potted plants were grown in a greenhouse at a day / night temperature setting of 29.5 / 26.7 ° C., and a 16 hour photoperiod was maintained with supplemental conditioning lighting. The test bowl was kept in the greenhouse until the test was completed.

  At the time of treatment, the test bowl was submerged to 3 cm above the soil surface and treated by applying the test compound directly to Inada water, and then the water depth was maintained during the test period. After 21 days, the effect of treatment on rice and weeds was assessed visually by comparison with untreated controls. The plant response assessments summarized in Table E are based on a scale of 0-100, with 0 being ineffective and 100 being complete suppression. A dash (-) response means no test result.

Test F
(Lawn) Cyandon dactylon, Kentucky bluegrass (Poa privacy), bentgrass (Agrostis palustris), bulls (hard)
fescue) (Festuca ovina), crabgrass (large crabgrass) (Digitaria sanguinalis), goosegrass (Eleusine indica), dallisgrass (dallisgrass) (Paspalum dilatatum), annual bluegrass (annual bluegrass) (Poa annua), chickweed (Stellaria media), Taraxacum officinale ( non-phytotoxic solution planted with seeds or small nuts of a plant species selected from dandelion (Taraxacum officinale), white clover (Trifolium repens) and Cyperus esculentus It was treated preemergence with test chemicals formulated in the mixture.

At the same time, plants selected from these crops and weed species were treated by post-emergence application of similarly formulated test chemicals. For post-emergence treatment, the plants ranged in height from 2 cm to 18 cm (1-4 leaf stage). Treated plants and controls were kept in the greenhouse for 12-14 days, after which all species were visually assessed compared to controls. The plant response assessments summarized in Table F are based on a scale of 0-100, with 0 being ineffective and 100 being complete suppression. A dash (-) response means no test result.

Test G
Cynodon dactylon (Cynodon dactylon), Surinam grass (Brachiaria decumbens), large crabgrass (Digitaria sanguinalis), green foxtail (Setaria viridis), goosegrass (Eleusine indica), Johnson grass (Sorghum halepense), Kokia (Kochia scoparia), beans morningglory (pitted morningglory) (Ipomoea launcosa), purple nutsedge (Cyperus rotundus), ragweed (Ambrosia elatior), black mustard (Brassica nigra), guinea egra Panicum maximum), dallisgrass (Paspalum dilatatum), barnyardgrass (Echinochloa crus-galli), Shinkurinoiga (southern sandbur) (Cenchrus echinatus), common Saw Di style (com
mon sowhistle (Sonchus oleraceus), American deer (pickly sida) (Sida spinosa), Italian ryegrass (Lolium multiflorum), common purr lane (ken) (Common groundsel) (Senecio vulgaris), chickweed (Stellaria media), tropical spiderwort (Commelina benghalensis), sparrow anemone (Poa annua) Yahiki (downy bromegrass) (Bromus tectorum), switch grass (itchgrass) (Rottboellia cochinchinensis), quackgrass (quackgrass) (Elytrigia repens), Erigeron canadensis (Canada
horseweed) (Conyza canadensis), field bindweed (Convolvulus arvensis), spinach needs (spanishedles) (Bidens bipinnata), vs. Seed seeds or small nuts were planted and pre-emergence treated with test chemicals formulated in a non-phytotoxic solvent mixture containing surfactant.

  At the same time, plants selected from these crops and weed species were treated by post-emergence application of several test agents formulated in the same way. For post-emergence treatment, the plants ranged in height from 2 cm to 18 cm (1-4 leaf stage). Treated plants and controls were kept in the greenhouse for 12-21 days, after which all species were visually assessed compared to controls.

  At another time, vines grown in a given container (grape (Vitus vinifera) vines), and olive (Olea europaea) and orange (orange) (Citrus sinensis) trees are similarly formulated, It was then treated with several test chemicals applied below the soil surface and 5 cm below the plant stem or stem (post-directed application). Plants ranged from 30 cm to 100 cm in height. Application was carried out using a hand spray delivering a volume of 990 L / ha. Treated plants and controls were kept in the greenhouse for 28 days, after which the treated plants were visually evaluated compared to the controls.

  At another time, seed pieces (nodes) of sugarcane (Saccharum officinarum) were planted and treated pre-emergence and / or post-emergence with several similarly formulated test agents. Treated plants and controls were kept in the greenhouse for 14 days, after which the treated plants were visually evaluated compared to the controls.

  The plant response assessments summarized in Table G are based on a scale of 0-100, with 0 being ineffective and 100 being complete suppression. A dash (-) response means no test result.

Test H
This test evaluated the effect of a mixture of Compound 1 and diflufenzopyr on several plant species. Dermatitis (DIGSA, Digitaria sanginalis (L.) Scop.), Shiroza (CHEAL, Chenopodium album L.), Agate (Emarum, reversal); -Galli (L.) Beauv.), Corn (ZEAMD, Zea Mays L. cv. "Pioneer 33G26"), Mallet (red) morning glory (IPOCO, Ipoomoa cocinea L. cv. Seteria Faberi Herrm.) Fine velvetleaf (ABUTH, Abutilon theophrasti Medik.) A more composed test plants seeds, Supagunamu peat moss (spaghnum peat moss)
Ready-Earth® planting medium (43041, Marysville, Ohio, Scottslawn Road 14111, Scotts Company, 14111 Scottslawn Road, Marysville, Ohio) Planted in a pot containing Ohio 43041)). Small seeded-species seeds were planted at a depth of about 1 cm, and larger seeds were planted at a depth of about 2.5 cm. Plants were grown in the greenhouse using auxiliary lighting to maintain a photoperiod of about 14 hours, and day and night temperatures were about 25-30 ° C. and 22-25 ° C., respectively. Compound fertilizer was applied through the watering system. The plants were grown for 7-11 days so that the plants were in the height range of 2-18 cm (1-4 leaf stage) during the treatment period. The treating agent, alone or in combination, consists of Compound 1 and diflufenzopyr, suspended or dissolved in an aqueous solvent comprising glycerin and Tween nonionic surfactant, and 541 L / ha. The volume was used as a foliage spray. Each treatment was repeated 4 times. The applied solvent was found to be ineffective compared to untreated test plants. For the first 24 hours after treatment, the treated plants and controls were kept in the greenhouse and given as much water as needed to avoid wetting the foliage. The effect in plants about 3 weeks after treatment was compared visually with untreated controls. Plant response assessments are calculated as the average of 4 iterations, based on a scale of 0-100, 0 is ineffective and 100 is complete inhibition. To determine the herbicidal effect expected from the mixture, the Colby's equation was used. Colby's equation (Colby, SR) "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations" Weed, 15 (Weeds) ), Pp. 20-22 (1967)), the expected additive effect of the herbicide mixture is calculated and for the two active ingredients:
P _{a + b} = P _a + P _b − (P _a P _b / 100)
Where P _{a + b} is the percentage effect of the mixture expected from the additive contribution of the individual components,
P _a is the observed percentage effect of the first active ingredient at the same usage rate as the mixture, and P _b is the observed percentage effect of the second active ingredient at the same usage rate as the mixture). is there.

  The additive effects expected from the results and the Colby equation are summarized in Table H.

  As can be seen from the results listed in Table H, most of the observations were larger than expected, calculated in some cases from the Colby equation, and in some cases very large. Most notable are the larger additive effects observed in bark, bark, corn and aquinocologosa. The increase is not significant for the other test species, but this was mainly because the expected effect at the rate tested was already almost 100%.

Test I
This test evaluated the effect of a mixture of compound 9 and metsulfuron-methyl and a mixture of compound 9 and 5: 1 by weight of chlorsulfuron and metsulfuron-methyl in several plant species. Wheat (TRZAW; Triticum)
aestivum), buckwheat (POLCO; Polygonum convolvulus), Aogateto (AMARE; Amaranthus retroflexus), Noharagara (SINAR; ), Kochia (KCHSC; Kochia scoparia) and Shiroza (CHEAL), the seeds of test plants were planted in loam soil and sand blends. Plants were grown in the greenhouse using auxiliary lighting to maintain a photoperiod of about 14 hours, and day and night temperatures were about 23 ° C. and 16 ° C., respectively. Compound fertilizer was applied through the watering system. The plants were grown for 10-23 days so that the plants were in the 2-8 leaf range during the treatment period. The treating agent, alone or in combination, consisted of Compound 9, metsulfuron-methyl, and chlorsulfuron-methsulfuron-methyl (5: 1). The treatment was formulated in a non-phytotoxic solvent mixture containing a surfactant and applied as a foliage spray using a volume of 280-458 L / ha. Each treatment was repeated three times. The applied solvent was found to be ineffective compared to untreated test plants. For the first 24 hours after treatment, the treated plants and controls were kept in the greenhouse and given as much water as needed to avoid wetting the foliage. The effect on plants about 17 days after treatment was visually compared with untreated controls. The plant response rating is calculated as the average of 3 replicates, based on a scale of 0-100, 0 is invalid and 100 is complete suppression. The Colby equation was used to determine the expected herbicidal effect from the mixture. The additive effects expected from the results and the Colby equation are summarized in Table I.

  As can be seen from the results listed in Table I, some observations on weeds were greater than expected from the Colby equation. Most notable are the larger additive effects observed in buckwheat, Kochia and Shiroza.

  In addition, observations on almost all treatments in wheat are lower than expected from the Colby equation, indicating crop safety.

Exam J
This test evaluated the effect of a mixture of compound 58 and azimusulfuron on several plant species. Three plastic bowls (about 16 cm in diameter) per evaluation, sterilized Tama silt soil with 35:50:15 ratio of sand, silt and clay, and 2.6% organic matter Was partially filled. The three pots planted individually were as follows. For each evaluation, seeds from the American American oak (HETLI; Heteranthera limosa), Tamagayatatsu (CYPDI; Cyperus diffformis) and Hosobahimemisohagi (AMMCO; Ammania coccinea) were planted in one 16 cm pot. For each evaluation, seeds from the United States Bared Sprung Top (LEFUF; Leptochloa fuscassp. Fascicularis), one stand of 9 or 10 rice seedlings (ORYSW; Oryza sativa cv. “Japonica-M202”) And one stand of 6 transplanted rice seedlings (ORYSP; Oryza sativa cv. “Japonica-M202”) were planted in one 16 cm pot. For each assessment, the United States canine fly (ECHCG; Echinochloa crus-galli), rate watergrass (ECOR2; Echinochloa oryzicola), early watergrass (ECHOR; Echinochloa oryzoides) and wasabi (ECHCO)
seeds from colona) were planted in one 16 cm pot. Planting was continuously carried out so that the crop and weed species were in the 2.0-2.5 leaf stage at the time of treatment.

  Potted plants were grown in a greenhouse at a day / night temperature setting of 29.5 / 26.7 ° C., and a 16 hour photoperiod was maintained with supplemental conditioning lighting. The test bowl was kept in the greenhouse until the test was completed.

  At the time of treatment, the test pots were submerged to 3 cm above the soil surface and then treated by directly applying the test compound formulated in a non-phytotoxic solvent mixture containing a surfactant to the rice field water. During the test period, the pots were maintained at a water depth of 3 cm. The treating agent was composed of Compound 58 and azimusulfuron alone or in combination. After 21 days, the effect of treatment on rice and weeds was assessed visually by comparison with untreated controls. Plant response assessments are calculated as the average of three replicates and are summarized in Table J. This evaluation is based on a scale of 0-100, where 0 is invalid and 100 is complete suppression. A dash (-) response means no test result. The Colby equation was used to determine the expected herbicidal effect from the mixture. The additive effects expected from the results and the Colby equation are summarized in Table J.

Test K
Surfactant contains seeds of plant species selected from sulfonylurea herbicide-sensitive (SU-sensitive) and sulfonylurea herbicide-resistant (SU-resistant) yamgra (GALAP; Galium aline) and wheat (TRZAW; Triticum aestivum) Treated by pre-emergence application of test chemicals formulated in a non-phytotoxic solvent mixture. For wheat and yamgra, plants were treated at the 2-3 leaf stage and the two-row stage, respectively. Treated plants and controls were kept in a controlled growth environment for 15 days, after which all species were visually assessed compared to controls. The plant response assessments summarized in Table K are based on a scale of 0-100, with 0 being ineffective and 100 being complete suppression. A dash (-) response means no test result.

  As can be seen from Table K, chlorsulfuron has little effect on the sulfonylurea resistant biotype of Galium apine in this study, while compounds 1 and 9 give good inhibition in both resistant and sensitive biotypes. It was.

Test L
Studies in this field included a treatment consisting of Compound 1 and nicosulfuron, alone or in combination, in Canada thistle (Cirsium arvense) and daisie flavane (Erigeron spp.). Plants ranged from 20 to 30 cm high at the time of application in May near Newark, Delaware. Compound 1 was formulated as a wettable powder containing 25% by weight of the active ingredient. Nicosulfuron was in the form of Accent (R) Herbide (Accent (R) Herbicide) in a water dispersible granule formulation containing 75% by weight of the active ingredient. Prior to treatment, the formulation was dispersed in water in a nebulizer tank. Processing was carried out using a backpack sprayer calculated to deliver 24 gallons per acre (224 L per hectare) to a 10 ft x 30 ft (3 m x 9 m) compartment. Each treatment was repeated twice. The effect on plants about 56 days after treatment was compared visually with untreated controls. Plant response assessments are calculated as the average of two replicates and are based on a scale of 0-100, where 0 is invalid and 100 is complete suppression. The Colby equation was used to determine the expected herbicidal effect from the mixture. The additive effects expected from the results and the Colby equation are summarized in Table L.

Table L shows that a synergistic effect is evident from the combination of Compound 1 and nicosulfuron in this study.

Claims (19)

Formula I

[Where:
R ¹ is cyclopropyl optionally substituted by 1 to 5 R ⁵ ,
R ² is ^{_{CO 2 R 12, CHO, C}} (= NOR 14) H, C (= NNR 48 R 49) H, (O) j C (R 15) (R 16) CO 2 R 17 or C (= O ) N (R ¹⁸ ) R ¹⁹
R ³ is halogen, OR ²⁰ , SR ²¹ or N (R ²² ) R ²³ ;
R ⁴ is —N (R ²⁴ ) R ²⁵ or —NO ₂ ;
Each R ⁵ is independently halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₁ -C ₃ alkoxy, C ₁ -C ₂ haloalkoxy, a C ₁ -C ₃ alkylthio or C ₁ -C ₂ haloalkylthio,
R ¹² is H, —CH— [C (O) O (CH ₂ ) _m ] —, —N═C (R ⁵⁵ ) R ⁵⁶ , or C ₁ -C ₁₄ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₄ -C ₁₂ alkylcycloalkyl, C ₄ -C ₁₂ cycloalkylalkyl, a C ₂ -C ₁₄ alkenyl, C ₂ -C ₁₄ group selected from an alkynyl and phenyl, one to three optionally each group R ¹² may be substituted by R ²⁷ , or R ¹² is a divalent group linking the respective carboxylate functional groups CO ₂ R ¹² of the two pyrimidine ring systems of formula I, The group is selected from —CH ₂ —, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ — and —CH (CH ₃ ) CH ₂ —;
R ¹⁴ is H, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or benzyl;
R ¹⁵ is H, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, hydroxy, C ₁ -C ₄ alkoxy or C ₂ -C ₄ alkylcarbonyloxy;
R ¹⁶ is H, halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl, or R ¹⁵ and R ¹⁶ are oxygen atoms, together with the carbon atom to which they are attached, a carbonyl moiety Form the
R ¹⁷ is C ₁ -C ₁₀ alkyl optionally substituted by 1 to 3 R ²⁹ , or benzyl;
R ¹⁸ is H, C ₁ -C ₄ alkyl, hydroxy, C ₁ -C ₄ alkoxy or S (O) ₂ R ⁵⁷ ,
R ¹⁹ is H or C ₁ -C ₄ alkyl;
R ²⁰ is H, C ₁ -C ₄ alkyl or C ₁ -C ₃ haloalkyl,
R ²¹ is H, C ₁ -C ₄ alkyl or C ₁ -C ₃ haloalkyl,
R ²² and R ²³ are independently H or C ₁ -C ₄ alkyl;
R ²⁴ is H, C ₁ -C ₄ alkyl optionally substituted by 1 to 2 R ³⁰ , C ₂ -C ₄ alkenyl optionally substituted by 1 to 2 R ³¹ Or C ₂ -C ₄ alkynyl optionally substituted by 1 to 2 R ³² , or R ²⁴ is C (═O) R ³³ , nitro, OR ³⁴ , S (O) _2. R ³⁵ , N (R ³⁶ ) R ³⁷ or N═C (R ⁶² ) R ⁶³ ,
R ²⁵ is H, C ₁ -C ₄ alkyl optionally substituted by 1 to 2 R ³⁰ or C (═O) R ³³ , or R ²⁴ and R ^{25 taken} together _{- (CH 2) 4 -,} - (CH 2) 5 -, - CH 2 CH = CHCH 2 - and _{- (CH 2) 2 O (} CH 2) 2 - is a group selected from where each group May optionally be substituted by 1 to 2 R ³⁸ , or R ²⁴ and R ²⁵ together may be ═C (R ³⁹ ) N (R ⁴⁰ ) R ⁴¹ or ═C (R ⁴² ) OR. ⁴³ ,
Each R ²⁷ is independently halogen, cyano, hydroxycarbonyl, C ₂ -C ₄ alkoxycarbonyl, hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, amino, C ₁ -C ₄ alkylamino, C ₂ -C _{4 dialkylamino, -CH- [O (CH 2)} n] - or optionally be substituted by one to three R ⁴⁴ Is good phenyl, or two R ²⁷ together are —OC (O) O— or —O (C (R ⁵⁸ ) (R ⁵⁸ )) _1-2 O—, or two R ²⁷ in the above form an oxygen atom together with the carbon atom to which they are bonded to form a carbonyl moiety,
Each R ²⁹ is independently halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, amino, C ₁ -C ₄ alkylamino or C a ₂ -C ₄ dialkylamino,
Each R ³⁰ , R ³¹ and R ³² is independently halogen, C ₁ -C ₃ alkoxy, C ₁ -C ₃ haloalkoxy, C ₁ -C ₃ alkylthio, C ₁ -C ₃ haloalkylthio, amino, C _1- C ₃ alkylamino, C ₂ -C ₄ dialkylamino or C ₂ -C ₄ alkoxycarbonyl,
Each R ³³ is independently H, C ₁ -C ₁₄ alkyl, C ₁ -C ₃ haloalkyl, C ₁ -C ₄ alkoxy, phenyl, phenoxy or benzyloxy;
R ³⁴ is H, C ₁ -C ₄ alkyl, C ₁ -C ₃ haloalkyl or CHR ⁶⁶ C (O) OR ⁶⁷ ;
R ³⁵ is C ₁ -C ₄ alkyl or C ₁ -C ₃ haloalkyl;
R ³⁶ is H, C ₁ -C ₄ alkyl or C (═O) R ⁶⁴ ,
R ³⁷ is H or C ₁ -C ₄ alkyl;
Each R ³⁸ is independently halogen, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, C ₁ -C ₃ haloalkoxy, C ₁ -C ₃ alkylthio, C ₁ -C ₃ haloalkylthio, amino, C ₁ -C ₃ alkylamino, a C ₂ -C ₄ dialkylamino or C ₂ -C ₄ alkoxycarbonyl,
R ³⁹ is H or C ₁ -C ₄ alkyl;
R ⁴⁰ and R ⁴¹ are independently H or C ₁ -C ₄ alkyl, or R ⁴⁰ and R ^{41 taken} together are — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, —CH ₂ CH═CHCH ₂ — or — (CH ₂ ) ₂ O (CH ₂ ) ₂ —,
R ⁴² is H or C ₁ -C ₄ alkyl;
R ⁴³ is C ₁ -C ₄ alkyl;
Each R ⁴⁴ is independently halogen, C ₁ -C ₄ alkyl, C ₁ -C ₃ haloalkyl, hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₃ haloalkoxy, C ₁ -C ₃ alkylthio, C _1- C ₃ haloalkylthio, amino, C ₁ -C ₃ alkylamino, C ₂ -C ₄ dialkylamino or nitro,
R ⁴⁸ is H, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkylcarbonyl, C ₂ -C ₄ alkoxycarbonyl or benzyl,
R ⁴⁹ is H, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl,
R ⁵⁵ and R ⁵⁶ are independently C ₁ -C ₄ alkyl;
R ⁵⁷ is C ₁ -C ₄ alkyl, C ₁ -C ₃ haloalkyl or NR ⁵⁹ R ⁶⁰ ,
Each R ⁵⁸ is independently selected from H and C ₁ -C ₄ alkyl;
R ⁵⁹ and R ⁶⁰ are independently H or C ₁ -C ₄ alkyl;
R ⁶² is H, C ₁ -C ₄ alkyl or phenyl optionally substituted by 1 to 3 R ⁶⁵ ;
R ⁶³ is H or C ₁ -C ₄ alkyl, or R ⁶² and R ⁶³ together are — (CH ₂ ) ₄ — or — (CH ₂ ) ₅ —;
R ⁶⁴ is H, C ₁ -C ₁₄ alkyl, C ₁ -C ₃ haloalkyl, C ₁ -C ₄ alkoxy, phenyl, phenoxy or benzyloxy;
Each R ⁶⁵ is independently CH ₃ , Cl or OCH ₃ ;
R ⁶⁶ is H, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy;
R ⁶⁷ is H, C ₁ -C ₄ alkyl or benzyl;
j is 0 or 1,
m is an integer from 2 to 3, and n is an integer from 1 to 4, a compound selected from N-oxides or agriculturally suitable salts thereof. The compound according to claim 1, wherein R ³ is halogen. 2. A compound according to claim 1 wherein R < ¹ > is cyclopropyl and R < ⁴ > is -N (R < ²⁴ >) R < ²⁵ >. A compound according to claim 3 R ² is CO ₂ R ^12, CHO or CH ₂ CO ₂ R ^17. R ²⁴ is H, C (O) R ³³ or C ₁ -C ₄ alkyl optionally substituted by R ³⁰ and R ²⁵ is H or C ₁ -C ₂ alkyl, or R ²⁴ And R ^{25 taken} together = C (R ³⁹ ) N (R ⁴⁰ ) R ⁴¹ . R ² is CO ₂ R ^12, and A compound according to claim 5 R ²⁴ and R ²⁵ are H. A compound according to claim 6 R ¹² is H, C ₁ ~C ₄ alkyl or benzyl. Methyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate,
Ethyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate,
Phenylmethyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate,
6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylic acid monosodium salt,
Methyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate,
Phenylmethyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate,
Claims selected from the group consisting of 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid monosodium salt and ethyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate Item 1. The compound according to Item 1.   A herbicidal amount comprising a herbicidally effective amount of the compound of claim 1 and an effective amount of at least one additional active ingredient selected from the group consisting of other herbicides and herbicide safeners. Agent mixture.   A herbicidal composition comprising a herbicidally effective amount of the compound of claim 1 and at least one of a surfactant, a solid diluent or a liquid diluent.   A herbicidally effective amount of the compound of claim 1, an effective amount of at least one additional active ingredient selected from the group consisting of other herbicides and herbicide safeners, a surfactant, A herbicidal composition comprising at least one of a solid diluent or a liquid diluent.   A compound which is 2-cyclopropyl-1,6-dihydro-6-oxo-4-pyrimidinecarboxylic acid.   A compound which is 5-chloro-2-cyclopropyl-1,6-dihydro-6-oxo-4-pyrimidinecarboxylic acid.   A compound that is 5,6-dichloro-2-cyclopropyl-4-pyrimidinecarboxylic acid. Methyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate,
Ethyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate,
Phenylmethyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate,
6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylic acid monosodium salt,
6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid,
Methyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate,
Phenylmethyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate,
6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid monosodium salt,
The method according to claim 1, selected from the group consisting of ethyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylic acid and ethyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate. The described compound.   A herbicidal amount comprising a herbicidally effective amount of the compound of claim 15 and an effective amount of at least one additional active ingredient selected from the group consisting of other herbicides and herbicide safeners. Agent mixture.   Additional active ingredients include amidosulfuron, azimusulfuron, bensulfuron-methyl, bispyribac, bispyrivac-sodium, chlorimuron-ethyl, chlorsulfuron, shinosulfuron, chloransram-methyl, cyclosulfamuron, diclosram, etamethsulfuron-methyl Ethoxysulfuron, flazasulfuron, flurosulfam, flurocarbazone, flurocarbazone-sodium, flucetosulfuron, flumetoslam, flupirsulfuron-methyl, flupirsulfuron-methyl-sodium, foramsulfuron, halosulfuron-methyl, imazametabenz-methyl, imazamox , Imazapic, imazapill, imazaquin, imazaquin-ammonium, imazetapyr, imazosulfuron, iodosulfuron-methyl, meso Ruflon-methyl, methoslam, metsulfuron-methyl, nicosulfuron, oxasulfuron, penoxsulam, primisulfuron-methyl, propoxycarbazone, propoxycarbazone-sodium, prosulfuron, pyrazosulfuron-ethyl, pyribenzoxime, pyriftalide, pyriminobac-methyl, Selected from the group consisting of pyrithiobac, pyrithiobac-sodium, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron-methyl, trisulfuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron-methyl and tritosulfuron A herbicide mixture according to claim 9. An additional active ingredient in combination with at least one other active ingredient,
Chlorsulfuron and furcarbazone-sodium;
Chlorsulfuron and sulfometuron-methyl;
Flumethoslam, nicosulfuron and rimsulfuron;
Mesosulfuron-methyl and iodosulfuron-methyl;
Metsulfuron-methyl and chlorsulfuron;
Metsulfuron-methyl and sulfomethuron-methyl;
Metsulfuron-methyl, thifensulfuron-methyl and tribenuron-methyl;
Imazapyr and metsulfuron-methyl;
Imazapyr, metsulfuron-methyl and sulfomethuron-methyl;
Imazapyr and sulfometuron-methyl;
Rimsulfuron and nicosulfuron;
Rimsulfuron and thifensulfuron-methyl;
Thifensulfuron-methyl and metsulfuron-methyl;
Tribenuron-methyl and metsulfuron-methyl;
Tribenuron-methyl and thifensulfuron-methyl;
18. A herbicide mixture according to claim 17, forming a combination of active ingredients selected from the group consisting of bensulfuron-methyl and metsulfuron-methyl; and metsulfuron-methyl and chlorimuron-ethyl.   A compound which is monopotassium salt of 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid.